Materials for Battery Electrolytes and Methods for Use

ABSTRACT

Described herein are materials for use in electrolytes that provide a number of desirable characteristics when implemented within batteries, such as high stability during battery cycling up to high temperatures high voltages, high discharge capacity, high coulombic efficiency, and excellent retention of discharge capacity and coulombic efficiency over several cycles of charging and discharging. In some embodiments, a high voltage electrolyte includes a base electrolyte and a set of additive compounds, which impart these desirable performance characteristics.

This application claims priority to and the benefit of each of thefollowing applications: U.S. Provisional Application No. 61/495,318filed Jun. 9, 2011 entitled “Battery Electrolytes for High VoltageCathode Materials”; U.S. Provisional Application No. 61/543,262 filedOct. 4, 2011 entitled “Battery Electrolytes for High Voltage CathodeMaterials”; and U.S. Provisional Application No. 61/597,509 filed Feb.10, 2012 entitled “Battery Electrolytes for High Voltage CathodeMaterials”; each of which applications are incorporated herein byreference.

BACKGROUND OF THE INVENTION

The invention relates generally to battery electrolytes. Moreparticularly, the invention relates to battery electrolytes to improvestability of batteries, such as one or more of high voltage stability,thermal stability, electrochemical stability, and chemical stability.

An electrolyte serves to transportions and prevent electrical contactbetween electrodes in a battery. Organic carbonate-based electrolytesare most commonly used in lithium-ion (“Li-ion”) batteries, and, morerecently, efforts have been made to develop new classes of electrolytesbased on sulfones, silanes, and nitriles. Unfortunately, theseconventional electrolytes typically cannot be operated at high voltages,since they are unstable above 4.5 V or other high voltages. At highvoltages, conventional electrolytes can decompose, for example, bycatalytic oxidation in the presence of cathode materials, to produceundesirable products that affect both the performance and safety of abattery.

In the case of Li-ion batteries, cobalt and nickel-containingphosphates, fluorophosphates, fluorosulphates, spinels, and silicateshave been reported to have higher energy densities than LiFePO₄,LiMn₂O₄, and other commonly used cathode materials. However, thesecathode materials also have redox potentials greater than 4.5 V,allowing for operation of the battery at higher voltages but alsopossibly causing severe electrolyte decomposition in the battery. Inorder to use a cathode material to deliver a higher energy density at ahigher voltage platform, the hurdle of electrolyte decomposition shouldbe addressed at least up to, or above, a redox potential of the cathodematerial.

Another problem with both organic carbonate-based electrolytes and otherclasses of electrolytes is chemical stability at elevated temperatures.Even at low voltages, elevated temperatures can cause conventionalelectrolytes to decompose, for example, by catalytic oxidation in thepresence of cathode materials, to produce undesirable products thataffect both performance and safety of a battery.

It is against this background that a need arose to develop theelectrolytes and related methods and systems described herein. Certainembodiments of the inventions disclosed herein address these and otherchallenges.

BRIEF SUMMARY

Certain embodiments of the invention are directed to a compound for usein an electrolyte and an electrolyte solution. The compound isrepresented by the formula (I):

R₁, R₂, R₃, R₄, R₅, and R₆ are independently selected from the groupconsisting of substituted and unsubstituted C₁-C₂₀ alkyl groups,substituted and unsubstituted C₁-C₂₀ alkenyl groups, substituted andunsubstituted C₁-C₂₀ alkynyl groups, and substituted and unsubstitutedC₅-C₂₀ aryl groups. X is selected from the group consisting of carbon,substituted and unsubstituted C₃-C₂₀ alkyl groups, substituted andunsubstituted C₂-C₂₀ alkenyl groups, and substituted and unsubstitutedC₄-C₂₀ alkynyl groups. In certain embodiments, the composition of claim1 wherein the compound is represented by the formula (II):

Certain embodiments of the invention are directed to an electrolytesolution including a salt, a solvent, and a compound represented byformula (I) and methods of making such an electrolyte solution. Certainembodiments of the invention are directed to an electrolyte solutionincluding a salt, a solvent, and a compound represented by formula (II)and methods of making such an electrolyte solution.

Other embodiments of the invention are directed to methods of forming,conditioning, and operating a battery including such high voltage andhigh temperature electrolyte solutions. For example, methods ofoperating or using a battery can include providing the battery, andcycling such battery to supply power for consumer electronics, portableelectronics, hybrid vehicles, electrical vehicles, power tools, powergrid, military applications, and aerospace applications. For example,methods of forming a battery can include providing an anode, providing acathode, and providing an electrolyte solution disposed between theanode and the cathode. The electrolyte can include an electrolytesolution of certain embodiments of the invention. The methods of formingthe battery can also include cycling the battery to convert astabilizing additive compound of the electrolyte into a derivativethereof.

Other aspects and embodiments of the invention are also contemplated.The foregoing summary and the following detailed description are notmeant to restrict the invention to any particular embodiment but aremerely meant to describe some embodiments of the invention.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

FIG. 1 illustrates a Li-ion battery implemented in accordance with anembodiment of the invention.

FIG. 2 illustrates the operation of a Li-ion battery and a graphicalrepresentation of an illustrative non-limiting mechanism of action of anelectrolyte including an additive compound, according to an embodimentof the invention.

FIG. 3A compares capacity retention with and without a stabilizingadditive over several cycles, and FIG. 3B compares coulombic efficiencywith and without the stabilizing additive over several cycles, accordingto an embodiment of the invention.

FIG. 4 compares capacity retention with and without a stabilizingadditive over several cycles at 25° C., according to an embodiment ofthe invention.

FIG. 5 superimposes results of measurements of capacity retention at 50°C. onto FIG. 4, according to an embodiment of the invention.

FIG. 6 is a plot of capacity retention at the 50th cycle as a functionof concentration of a stabilizing additive, according to an embodimentof the invention.

FIG. 7 is a plot of coulombic efficiency at the 50^(th) cycle as afunction of concentration of a stabilizing additive, according to anembodiment of the invention.

FIG. 8 sets forth superimposed cyclic voltammograms for the 1^(st) cyclethrough the 3^(rd) cycle. according to an embodiment of the invention.

FIG. 9 sets forth superimposed cyclic voltammograms for the 4^(th) cyclethrough the 6^(th) cycle, according to an embodiment of the invention.

FIG. 10 compares capacity retention with and without a stabilizingadditive over several cycles after aging, according to an embodiment ofthe invention.

FIG. 11 compares capacity retention with and without a stabilizingadditive over several cycles at 50° C. for a LiMn_(1.5) Ni_(0.5)O₄cathode material, according to an embodiment of the invention.

FIG. 12 compares capacity retention with and without a stabilizingadditive over several cycles at 50° C. for a LiMn₂O₄ cathode material,according to an embodiment of the invention.

FIG. 13 sets forth open circuit voltage measurements at 50° C.,according to an embodiment of the invention.

FIG. 14 sets forth residual current measurements at a constant voltageat 50° C., according to an embodiment of the invention.

FIG. 15 compares capacity retention with and without a stabilizingadditive over several cycles, according to an embodiment of theinvention.

FIG. 16 compares capacity retention with stabilizing additives includingsilicon and stabilizing additives lacking silicon, according to anembodiment of the invention.

FIG. 17 compares specific capacity upon discharge at the 50^(th) cyclefor battery cells including various silicon-containing stabilizingadditives, according to an embodiment of the invention.

FIG. 18 compares capacity retention of silicon-containing stabilizingadditives over several cycles, according to an embodiment of theinvention.

FIG. 19 compares specific capacity upon discharge at the 100^(th) cyclewith and without silicon-containing stabilizing additives inconventional electrolytes, according to an embodiment of the invention.

FIG. 20 compares specific capacity upon discharge at differenttemperatures with and without a silicon-containing stabilizing additive,according to an embodiment of the invention.

FIG. 21 compares capacity retention at the 25^(th) cycle with andwithout a silicon-containing stabilizing additive for various cathodematerials, according to an embodiment of the invention.

FIG. 22 sets forth residual current measurements for battery cells heldat about 4.5V, about 4.9V, and about 5.1V for about 10 hours at 50degrees C., according to an embodiment of the invention.

FIG. 23 compares coulombic efficiency with and without a stabilizingadditive over several cycles for a LiMn_(0.5)Ni_(0.5)O₄ cathodematerial, according to an embodiment of the invention.

FIG. 24 compares specific capacity upon discharge with and without astabilizing additive over several cycles after storage at 50 degrees C.for 8 days for a doped LiCoPO₄ cathode material, according to anembodiment of the invention.

FIG. 25 compares capacity retention with and without a stabilizingadditive at different charging and discharging rates, according to anembodiment of the invention.

FIG. 26 compares capacity retention with and without a stabilizingadditive at room temperature for a LiMn_(0.5)Ni_(0.5)O₄ cathodematerial, according to an embodiment of the invention.

FIG. 27 sets forth voltage profiles at the 1^(st) and 100^(th) cyclesduring charging with and without a stabilizing additive, according to anembodiment of the invention.

FIG. 28 sets forth voltage profiles at the 3^(rd) cycle duringdischarging with and without a stabilizing additive, according to anembodiment of the invention.

FIG. 29 compares coulombic efficiency of battery cells with and withoutstabilizing additives at the first cycle.

FIG. 30 compares capacity retention of the battery cells with andwithout stabilizing additives over several cycles, expressed in terms ofa percentage of an initial specific capacity upon discharge retained ata particular cycle, according to an embodiment of the invention.

FIG. 31 compares capacity retention of the battery cells with andwithout stabilizing additives over several cycles, expressed in terms ofa percentage of an initial specific capacity upon discharge retained ata particular cycle, according to an embodiment of the invention.

FIG. 32 compares coulombic efficiency of the battery cells with andwithout stabilizing additives at the first cycle, according to anembodiment of the invention.

FIG. 33 compares capacity retention of the battery cells with andwithout stabilizing additives over several cycles, expressed in terms ofa percentage of an initial specific capacity upon discharge retained ata particular cycle, according to an embodiment of the invention.

FIG. 34 compares coulombic efficiency of the battery cells with andwithout stabilizing additives at the first cycle, according to anembodiment of the invention.

FIG. 35 compares coulombic efficiency of the battery cells with andwithout stabilizing additives at the first cycle, according to anembodiment of the invention.

FIGS. 36 through 43 compare capacity retention of the battery cells withand without stabilizing additives over several cycles, expressed interms of a percentage of an initial specific capacity upon dischargeretained at a particular cycle, according to an embodiment of theinvention.

FIG. 44 compares energy efficiency of the battery cells with and withoutstabilizing additives over several cycles, according to an embodiment ofthe invention.

FIG. 45 and FIG. 46 compare capacity retention of the battery cells withand without stabilizing additives over several cycles, expressed interms of a percentage of an initial specific capacity upon dischargeretained at a particular cycle, according to an embodiment of theinvention.

DETAILED DESCRIPTION OF THE INVENTION

The following definitions apply to some of the aspects described withrespect to some embodiments of the invention. These definitions maylikewise be expanded upon herein. Each term is further explained andexemplified throughout the description, figures, and examples. Anyinterpretation of the terms in this description should take into accountthe full description, figures, and examples presented herein.

As used herein, the singular terms “a,” “an,” and “the” include theplural referents unless the context clearly dictates otherwise. Thus,for example, reference to an object can include multiple objects unlessthe context clearly dictates otherwise.

As used herein, the term “set” refers to a collection of one or moreobjects. Thus, for example, a set of objects can include a single objector multiple objects. Objects of a set also can be referred to as membersof the set. Objects of a set can be the same or different. In someinstances, objects of a set can share one or more commoncharacteristics.

As used herein, the terms “substantially” and “substantial” refer to aconsiderable degree or extent. When used in conjunction with an event orcircumstance, the terms can refer to instances in which the event orcircumstance occurs precisely as well as instances in which the event orcircumstance occurs to a close approximation, such as accounting fortypical tolerance levels or variability of the embodiments describedherein.

As used herein, the term “sub-micron range” refers to a general range ofdimensions less than about 1 μm or less than about 1,000 nm, such asless than about 999 nm, less than about 900 nm, less than about 800 nm,less than about 700 nm, less than about 600 nm, less than about 500 nm,less than about 400 nm, less than about 300 nm, or less than about 200nm, and down to about 1 nm or less. In some instances, the term canrefer to a particular sub-range within the general range, such as fromabout 1 nm to about 100 nm, from about 100 nm to about 200 nm, fromabout 200 nm to about 300 nm, from about 300 nm to about 400 nm, fromabout 400 nm to about 500 nm, from about 500 nm to about 600 nm, fromabout 600 nm to about 700 nm, from about 700 nm to about 800 nm, fromabout 800 nm to about 900 nm, or from about 900 nm to about 999 nm.

As used herein, the term “main group element” refers to a chemicalelement in any of Group IA (or Group 1), Group IIA (or Group 2), GroupIIIA (or Group 13), Group IVA (or Group 14), Group VA (or Group 15),Group VIA (or Group 16), Group VIIA (or Group 17), and Group VIIIA (orGroup 18). A main group element is also sometimes referred to as as-block element or a p-block element.

As used herein, the term “transition metal” refers to a chemical elementin any of Group IVB (or Group 4), Group VB (or Group 5), Group VIB (orGroup 6), Group VIIB (or Group 7), Group VIIIB (or Groups 8, 9, and 10),Group IB (or Group 11), and Group IIB (or Group 12). A transition metalis also sometimes referred to as a d-block element.

As used herein, the term “rare earth element” refers to any of Sc, Y,La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.

As used herein, the term “halogen” refers to any of F, Cl, Br, I, andAt.

As used herein, the term “chalcogen” refers to any of O, S, Se, Te, andPo.

As used herein, the term “heteroatom” refers to any atom that is not acarbon atom or a hydrogen atom. Examples of heteroatoms include atoms ofhalogens, chalcogens, Group IIIA (or Group 13) elements, Group IVA (orGroup 14) elements other than carbon, and Group VA (or Group 15)elements.

As used herein, the term “alkane” refers to a saturated hydrocarbon,including the more specific definitions of “alkane” herein. For certainembodiments, an alkane can include from 1 to 100 carbon atoms. The term“lower alkane” refers to an alkane that includes from 1 to 20 carbonatoms, such as from 1 to 10 carbon atoms, while the term “upper alkane”refers to an alkane that includes more than 20 carbon atoms, such asfrom 21 to 100 carbon atoms. The term “branched alkane” refers to analkane that includes one or more branches, while the term “unbranchedalkane” refers to an alkane that is straight-chained. The term“cycloalkane” refers to an alkane that includes one or more ringstructures. The term “heteroalkane” refers to an alkane that has one ormore of its carbon atoms replaced by one or more heteroatoms, such as N,Si, S, O, F, and P. The term “substituted alkane” refers to an alkanethat has one or more of its hydrogen atoms replaced by one or moresubstituent groups, such as halo groups, while the term “unsubstitutedalkane” refers to an alkane that lacks such substituent groups.Combinations of the above terms can be used to refer to an alkane havinga combination of characteristics. For example, the term “branched loweralkane” can be used to refer to an alkane that includes from 1 to 20carbon atoms and one or more branches. Examples of alkanes includemethane, ethane, propane, cyclopropane, butane, 2-methylpropane,cyclobutane, and charged, hetero, or substituted forms thereof.

As used herein, the term “alkyl group” refers to a monovalent form of analkane, including the more specific definitions of “alkyl” herein. Forexample, an alkyl group can be envisioned as an alkane with one of itshydrogen atoms removed to allow bonding to another group. The term“lower alkyl group” refers to a monovalent form of a lower alkane, whilethe term “upper alkyl group” refers to a monovalent form of an upperalkane. The term “branched alkyl group” refers to a monovalent form of abranched alkane, while the term “unbranched alkyl group” refers to amonovalent form of an unbranched alkane. The term “cycloalkyl group”refers to a monovalent form of a cycloalkane, and the term “heteroalkylgroup” refers to a monovalent form of a heteroalkane. The term“substituted alkyl group” refers to a monovalent form of a substitutedalkane, while the term “unsubstituted alkyl group” refers to amonovalent form of an unsubstituted alkane. Examples of alkyl groupsinclude methyl, ethyl, n-propyl, isopropyl, cyclopropyl, butyl,isobutyl, t-butyl, cyclobutyl, and charged, hetero, or substituted formsthereof.

As used herein, the term “alkylene group” refers to a bivalent form ofan alkane, including the more specific definitions of “alkylene group”herein. For example, an alkylene group can be envisioned as an alkanewith two of its hydrogen atoms removed to allow bonding to one or moreadditional groups. The term “lower alkylene group” refers to a bivalentform of a lower alkane, while the term “upper alkylene group” refers toa bivalent form of an upper alkane. The term “branched alkylene group”refers to a bivalent form of a branched alkane, while the term“unbranched alkylene group” refers to a bivalent form of an unbranchedalkane. The term “cycloalkylene group” refers to a bivalent form of acycloalkane, and the term “heteroalkylene group” refers to a bivalentform of a heteroalkane. The term “substituted alkylene group” refers toa bivalent form of a substituted alkane, while the term “unsubstitutedalkylene group” refers to a bivalent form of an unsubstituted alkane.Examples of alkylene groups include methylene, ethylene, propylene,2-methylpropylene, and charged, hetero, or substituted forms thereof.

As used herein, the term “alkene” refers to an unsaturated hydrocarbonthat includes one or more carbon-carbon double bonds, including the morespecific definitions of “alkene” herein. For certain embodiments, analkene can include from 2 to 100 carbon atoms. The term “lower alkene”refers to an alkene that includes from 2 to 20 carbon atoms, such asfrom 2 to 10 carbon atoms, while the term “upper alkene” refers to analkene that includes more than 20 carbon atoms, such as from 21 to 100carbon atoms. The term “cycloalkene” refers to an alkene that includesone or more ring structures. The term “heteroalkene” refers to an alkenethat has one or more of its carbon atoms replaced by one or moreheteroatoms, such as N, Si, S, O, F, and P. The term “substitutedalkene” refers to an alkene that has one or more of its hydrogen atomsreplaced by one or more substituent groups, such as halo groups, whilethe term “unsubstituted alkene” refers to an alkene that lacks suchsubstituent groups. Combinations of the above terms can be used to referto an alkene having a combination of characteristics. For example, theterm “substituted lower alkene” can be used to refer to an alkene thatincludes from 1 to 20 carbon atoms and one or more substituent groups.Examples of alkenes include ethene, propene, cyclopropene, 1-butene,trans-2 butene, cis-2-butene, 1,3-butadiene, 2-methylpropene,cyclobutene, and charged, hetero, or substituted forms thereof.

As used herein, the term “alkenyl group” refers to a monovalent form ofan alkene, including the more specific definitions of “alkenyl group”herein. For example, an alkenyl group can be envisioned as an alkenewith one of its hydrogen atoms removed to allow bonding to anothergroup. The term “lower alkenyl group” refers to a monovalent form of alower alkene, while the term “upper alkenyl group” refers to amonovalent form of an upper alkene. The term “cycloalkenyl group” refersto a monovalent form of a cycloalkene, and the term “heteroalkenylgroup” refers to a monovalent form of a heteroalkene. The term“substituted alkenyl group” refers to a monovalent form of a substitutedalkene, while the term “unsubstituted alkenyl group” refers to amonovalent form of an unsubstituted alkene. Examples of alkenyl groupsinclude ethenyl, 2-propenyl (i.e., allyl), isopropenyl, cyclopropenyl,butenyl, isobutenyl, t-butenyl, cyclobutenyl, and charged, hetero, orsubstituted forms thereof.

As used herein, the term “alkenylene group” refers to a bivalent form ofan alkene, including the more specific definitions of “alkenylene group”herein. For example, an alkenylene group can be envisioned as an alkenewith two of its hydrogen atoms removed to allow bonding to one or moreadditional groups. The term “lower alkenylene group” refers to abivalent form of a lower alkene, while the term “upper alkenylene group”refers to a bivalent form of an upper alkene. The term “cycloalkenylenegroup” refers to a bivalent form of a cycloalkene, and the term“heteroalkenylene group” refers to a bivalent form of a heteroalkene.The term “substituted alkenylene group” refers to a bivalent form of asubstituted alkene, while the term “unsubstituted alkenylene group”refers to a bivalent form of an unsubstituted alkene. Examples ofalkenyl groups include ethenylene, propenylene, 2-methylpropenylene, andcharged, hetero, or substituted forms thereof.

As used herein, the term “alkyne” refers to an unsaturated hydrocarbonthat includes one or more carbon-carbon triple bonds, including the morespecific definitions of “alkyne” herein. In some embodiments, an alkynecan also include one or more carbon-carbon double bonds. For certainembodiments, an alkyne can include from 2 to 100 carbon atoms. The term“lower alkyne” refers to an alkyne that includes from 2 to 20 carbonatoms, such as from 2 to 10 carbon atoms, while the term “upper alkyne”refers to an alkyne that includes more than 20 carbon atoms, such asfrom 21 to 100 carbon atoms. The term “cycloalkyne” refers to an alkynethat includes one or more ring structures. The term “heteroalkyne”refers to an alkyne that has one or more of its carbon atoms replaced byone or more heteroatoms, such as N, Si, S, O, F, and P. The term“substituted alkyne” refers to an alkyne that has one or more of itshydrogen atoms replaced by one or more substituent groups, such as halogroups, while the term “unsubstituted alkyne” refers to an alkyne thatlacks such substituent groups. Combinations of the above terms can beused to refer to an alkyne having a combination of characteristics. Forexample, the term “substituted lower alkyne” can be used to refer to analkyne that includes from 1 to 20 carbon atoms and one or moresubstituent groups. Examples of alkynes include ethyne (i.e.,acetylene), propyne, 1-butyne, 1-buten-3-yne, 1-pentyne, 2-pentyne,3-penten-1-yne, 1-penten-4-yne, 3-methyl-1-butyne, and charged, hetero,or substituted forms thereof.

As used herein, the term “alkynyl group” refers to a monovalent form ofan alkyne, including the more specific definitions of “alkynyl group”herein. For example, an alkynyl group can be envisioned as an alkynewith one of its hydrogen atoms removed to allow bonding to anothergroup. The term “lower alkynyl group” refers to a monovalent form of alower alkyne, while the term “upper alkynyl group” refers to amonovalent form of an upper alkyne. The term “cycloalkynyl group” refersto a monovalent form of a cycloalkyne, and the term “heteroalkynylgroup” refers to a monovalent form of a heteroalkyne. The term“substituted alkynyl group” refers to a monovalent form of a substitutedalkyne, while the term “unsubstituted alkynyl group” refers to amonovalent form of an unsubstituted alkyne. Examples of alkynyl groupsinclude ethynyl, propynyl, isopropynyl, butynyl, isobutynyl, t-butynyl,and charged, hetero, or substituted forms thereof.

As used herein, the term “alkynylene group” refers to a bivalent form ofan alkyne, including the more specific definitions of “alkynylene group”herein. For example, an alkynylene group can be envisioned as an alkynewith two of its hydrogen atoms removed to allow bonding to one or moreadditional groups of a molecule. The term “lower alkynylene group”refers to a bivalent form of a lower alkyne, while the term “upperalkynylene group” refers to a bivalent form of an upper alkyne. The term“cycloalkynylene group” refers to a bivalent form of a cycloalkyne, andthe term “heteroalkynylene group” refers to a bivalent form of aheteroalkyne. The term “substituted alkynylene group” refers to abivalent form of a substituted alkyne, while the term “unsubstitutedalkynylene group” refers to a bivalent form of an unsubstituted alkyne.Examples of alkynylene groups include ethynylene, propynylene,1-butynylene, 1-buten-3-ynylene, and charged, hetero, or substitutedforms thereof.

As used herein, the term “arene” refers to an aromatic hydrocarbon,including the more specific definitions of “arene” herein. For certainembodiments, an arene can include from 5 to 100 carbon atoms. The term“lower arene” refers to an arene that includes from 5 to 20 carbonatoms, such as from 5 to 14 carbon atoms, while the term “upper arene”refers to an arene that includes more than 20 carbon atoms, such as from21 to 100 carbon atoms. The term “monocyclic arene” refers to an arenethat includes a single aromatic ring structure, while the term“polycyclic arene” refers to an arene that includes more than onearomatic ring structure, such as two or more aromatic ring structuresthat are bonded via a carbon-carbon bond or that are fused together. Theterm “heteroarene” refers to an arene that has one or more of its carbonatoms replaced by one or more heteroatoms, such as N, Si, S, O, F, andP. The term “substituted arene” refers to an arene that has one or moreof its hydrogen atoms replaced by one or more substituent groups, suchas alkyl groups, alkenyl groups, alkynyl groups, halo groups, hydroxygroups, alkoxy groups, alkenoxy groups, alkynoxy groups, aryloxy groups,carboxy groups, cyano groups, nitro groups, amino groups, N-substitutedamino groups, silyl groups, and siloxy groups, while the term“unsubstituted arene” refers to an arene that lacks such substituentgroups. Combinations of the above terms can be used to refer to an arenehaving a combination of characteristics. For example, the term“monocyclic lower alkene” can be used to refer to an arene that includesfrom 5 to 20 carbon atoms and a single aromatic ring structure. Examplesof arenes include benzene, biphenyl, naphthalene, anthracene, pyridine,pyridazine, pyrimidine, pyrazine, quinoline, isoquinoline, and charged,hetero, or substituted forms thereof.

As used herein, the term “aryl group” refers to a monovalent form of anarene, including the more specific definitions of “aryl group” herein.For example, an aryl group can be envisioned as an arene with one of itshydrogen atoms removed to allow bonding to another group. The term“lower aryl group” refers to a monovalent form of a lower arene, whilethe term “upper aryl group” refers to a monovalent form of an upperarene. The term “monocyclic aryl group” refers to a monovalent form of amonocyclic arene, while the term “polycyclic aryl group” refers to amonovalent form of a polycyclic arene. The term “heteroaryl group”refers to a monovalent form of a heteroarene. The term “substituted arylgroup” refers to a monovalent form of a substituted arene, while theterm “unsubstituted arene group” refers to a monovalent form of anunsubstituted arene. Examples of aryl groups include phenyl, biphenylyl,naphthyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl,isoquinolyl, and charged, hetero, or substituted forms thereof.

As used herein, the term “imine” refers to an organic compound thatincludes one or more carbon-nitrogen double bonds, including the morespecific definitions of “imine” herein. For certain embodiments, animine can include from 1 to 100 carbon atoms. The term “lower imine”refers to an imine that includes from 1 to 20 carbon atoms, such as from1 to 10 carbon atoms, while the term “upper imine” refers to an iminethat includes more than 20 carbon atoms, such as from 21 to 100 carbonatoms. The term “cycloimine” refers to an imine that includes one ormore ring structures. The term “heteroimine” refers to an imine that hasone or more of its carbon atoms replaced by one or more heteroatoms,such as N, Si, S, O, F, and P. The term “substituted imine” refers to animine that has one or more of its hydrogen atoms replaced by one or moresubstituent groups, such as halo groups, while the term “unsubstitutedimine” refers to an imine that lacks such substituent groups.Combinations of the above terms can be used to refer to an imine havinga combination of characteristics. For example, the term “substitutedlower imine” can be used to refer to an imine that includes from 1 to 20carbon atoms and one or more substituent groups. Examples of iminesinclude R₁CH═NR₂, where R₁ and R₂ are independently selected fromhydride groups, alkyl groups, alkenyl groups, and alkynyl groups.

As used herein, the term “iminyl group” refers to a monovalent form ofan imine, including the more specific definitions of “iminyl” herein.For example, an iminyl group can be envisioned as an imine with one ofits hydrogen atoms removed to allow bonding to another group. The term“lower iminyl group” refers to a monovalent form of a lower imine, whilethe term “upper iminyl group” refers to a monovalent form of an upperimine. The term “cycloiminyl group” refers to a monovalent form of acycloimine, and the term “heteroiminyl group” refers to a monovalentform of a heteroimine. The term “substituted iminyl group” refers to amonovalent form of a substituted imine, while the term “unsubstitutediminyl group” refers to a monovalent form of an unsubstituted imine.Examples of iminyl groups include —R₁CH═NR₂, R₃CH═NR₄—, —CH═NR₅, andR₆CH═N—, where R₁, and R₄ are independently selected from alkylenegroups, alkenylene groups, and alkynylene groups, and R₂, R₃, R₅, and R₆are independently selected from hydride groups, alkyl groups, alkenylgroups, and alkynyl groups.

As used herein, the term “alcohol” refers to an organic compound thatincludes one or more hydroxy groups. For certain embodiments, an alcoholcan also be referred to as a substituted hydrocarbon, such as asubstituted arene that has one or more of its hydrogen atoms replaced byone or more hydroxy groups. Examples of alcohols include ROH, where R isselected from alkyl groups, alkenyl groups, alkynyl groups, and arylgroups.

As used herein, the term “ketone” refers to a molecule that includes oneor more groups of the form: —CO—. Examples of ketones include R₁—CO—R₂,where R₁ and R₂ are independently selected from alkyl groups, alkenylgroups, alkynyl groups, and aryl groups, and R₃—CO—R₄—CO—R₅, where R₃and R₅ are independently selected from alkyl groups, alkenyl groups,alkynyl groups, and aryl groups, and R₄ is selected from alkylenegroups, alkenylene groups, and alkynylene groups.

As used herein, the term “carboxylic acid” refers to an organic compoundthat includes one or more carboxy groups. For certain embodiments, acarboxylic acid can also be referred to as a substituted hydrocarbon,such as a substituted arene that has one or more of its hydrogen atomsreplaced by one or more carboxy groups. Examples of carboxylic acidsinclude RCOOH, where R is selected from alkyl groups, alkenyl groups,alkynyl groups, and aryl groups.

As used herein, the term “hydride group” refers to —H.

As used herein, the term “halo group” refers to —X, where X is ahalogen. Examples of halo groups include fluoro, chloro, bromo, andiodo.

As used herein, the term “hydroxy group” refers to —OH.

As used herein, the term “alkoxy group” refers to —OR, where R is analkyl group.

As used herein, the term “alkenoxy group” refers to —OR, where R is analkenyl group.

As used herein, the term “alkynoxy group” refers to —OR, where R is analkynyl group.

As used herein, the term “aryloxy group” refers to —OR, where R is anaryl group.

As used herein, the term “carboxy group” refers to —COOH.

As used herein, the term “alkylcarbonyloxy group” refers to RCOO—, whereR is an alkyl group.

As used herein, the term “alkenylcarbonyloxy group” refers to RCOO—,where R is an alkenyl group.

As used herein, the term “alkynylcarbonyloxy group” refers to RCOO—,where R is an alkynyl group.

As used herein, the term “arylcarbonyloxy group” refers to RCOO—, whereR is an aryl group.

As used herein, the term “thio group” refers to —SH.

As used herein, the term “alkylthio group” refers to —SR, where R is analkyl group.

As used herein, the term “alkenylthio group” refers to —SR, where R isan alkenyl group.

As used herein, the term “alkynylthio group” refers to —SR, where R isan alkynyl group.

As used herein, the term “arylthio group” refers to —SR, where R is anaryl group.

As used herein, the term “cyano group” refers to —CN.

As used herein, the term “nitro group” refers to —NO₂.

As used herein, the term “amino group” refers to —NH₂.

As used herein, the term “N-substituted amino group” refers to an aminogroup that has one or more of its hydrogen atoms replaced by one or moresubstituent groups. Examples of N-substituted amino groups include—NR₁R₂, where R₁ and R₂ are independently selected from hydride groups,alkyl groups, alkenyl groups, alkynyl groups, and aryl groups, and atleast one of R₁ and R₂ is not a hydride group.

As used herein, the term “alkylcarbonylamino group” refers to —NHCOR,where R is an alkyl group.

As used herein, the term “N-substituted alkylcarbonylamino group” refersto an alkylcarbonylamino group that has its hydrogen atom replaced by asubstituent group. Examples of N-substituted alkylcarbonylamino groupsinclude —NR₁COR₂, where R₁ is selected from alkyl groups, alkenylgroups, alkynyl groups, and aryl groups, and R₂ is an alkyl group.

As used herein, the term “alkenylcarbonylamino group” refers to —NHCOR,where R is an alkenyl group.

As used herein, the term “N-substituted alkenylcarbonylamino group”refers to an alkenylcarbonylamino group that has its hydrogen atomreplaced by a substituent group. Examples of N-substitutedalkenylcarbonylamino groups include —NR₁COR₂, where R₁ is selected fromalkyl groups, alkenyl groups, alkynyl groups, and aryl groups, and R₂ isan alkenyl group.

As used herein, the term “alkynylcarbonylamino group” refers to —NHCOR,where R is an alkynyl group.

As used herein, the term “N-substituted alkynylcarbonylamino group”refers to an alkynylcarbonylamino group that has its hydrogen atomreplaced by a substituent group. Examples of N-substitutedalkynylcarbonylamino groups include —NR₁COR₂, where R₁ is selected fromalkyl groups, alkenyl groups, alkynyl groups, and aryl groups, and R₂ isan alkynyl group.

As used herein, the term “arylcarbonylamino group” refers to —NHCOR,where R is an aryl group.

As used herein, the term “N-substituted arylcarbonylamino group” refersto an arylcarbonylamino group that has its hydrogen atom replaced by asubstituent group. Examples of N-substituted arylcarbonylamino groupsinclude —NR₁COR₂, where R₁ is selected from alkyl groups, alkenylgroups, alkynyl groups, and aryl groups, and R₂ is an aryl group.

As used herein, the term “silyl group” refers to —SiR₁R₂R₃, where R₁,R₂, and R₃ are independently selected from, for example, hydride groups,alkyl groups, alkenyl groups, alkynyl groups, and aryl groups.

As used herein, the term “siloxy group” refers to —OSiR₁R₂R₃, where R₁,R₂, and R₃ are independently selected from, for example, hydride groups,alkyl groups, alkenyl groups, alkynyl groups, and aryl groups.

As used herein, the term “ether linkage” refers to —O—.

As used herein, the term “specific capacity” refers to the amount (e.g.,total or maximum amount) of electrons or lithium ions a material is ableto hold (or discharge) per unit mass and can be expressed in units ofmAh/g. In certain aspects and embodiments, specific capacity can bemeasured in a constant current discharge (or charge) analysis whichincludes discharge (or charge) at a defined rate over a defined voltagerange against a defined counterelectrode. For example, specific capacitycan be measured upon discharge at a rate of about 0.05 C (e.g., about7.5 mA/g) from 4.95 V to 2.0 V versus a Li/Li⁺ counterelectrode. Otherdischarge rates and other voltage ranges also can be used, such as arate of about 0.1 C (e.g., about 15 mA/g), or about 0.5 C (e.g., about75 mA/g), or about 1.0 C (e.g., about 150 mA/g).

As used herein, a rate “C” refers to either (depending on context) thedischarge current as a fraction or multiple relative to a “1 C” currentvalue under which a battery (in a substantially fully charged state)would substantially fully discharge in one hour, or the charge currentas a fraction or multiple relative to a “1 C” current value under whichthe battery (in a substantially fully discharged state) wouldsubstantially fully charge in one hour.

As used herein, the terms “cycle” or “cycling” refer to complementarydischarging and charging processes.

As used herein, the term “rated charge voltage” refers to an upper endof a voltage range during operation of a battery, such as a maximumvoltage during charging, discharging, and/or cycling of the battery. Insome aspects and some embodiments, a rated charge voltage refers to amaximum voltage upon charging a battery from a substantially fullydischarged state through its (maximum) specific capacity at an initialcycle, such as the 1^(st) cycle, the 2^(nd) cycle, or the 3^(rd) cycle.In some aspects and some embodiments, a rated charge voltage refers to amaximum voltage during operation of a battery to substantially maintainone or more of its performance characterics, such as one or more ofcoulombic efficiency, retention of specific capacity, retention ofenergy density, and rate capability.

As used herein, the term “rated cut-off voltage” refers to a lower endof a voltage range during operation of a battery, such as a minimumvoltage during charging, discharging, and/or cycling of the battery. Insome aspects and some embodiments, a rated cut-off voltage refers to aminimum voltage upon discharging a battery from a substantially fullycharged state through its (maximum) specific capacity at an initialcycle, such as the 1^(st) cycle, the 2^(nd) cycle, or the 3^(rd) cycle,and, in such aspects and embodiments, a rated cut-off voltage also canbe referred as a rated discharge voltage. In some aspects and someembodiments, a rated cut-off voltage refers to a minimum voltage duringoperation of a battery to substantially maintain one or more of itsperformance characterics, such as one or more of coulombic efficiency,retention of specific capacity, retention of energy density, and ratecapability.

As used herein, the “maximum voltage” refers to the voltage at whichboth the anode and the cathode are fully charged. In an electrochemicalcell, each electrode may have a given specific capacity and one of theelectrodes will be the limiting electrode such that one electrode willbe fully charged and the other will be as fully charged as it can be forthat specific pairing of electrodes. The process of matching thespecific capacities of the electrodes to achieve the desired capacity ofthe electrochemical cell is “capacity matching.”

To the extent certain battery characteristics can vary with temperature,such characteristics are specified at room temperature (25° C.), unlessthe context clearly dictates otherwise.

Certain embodiments of the invention relate to electrolyte solutionsthat provide a number of desirable characteristics when implementedwithin batteries, such as high stability during battery cycling to highvoltages at or above 4.2 V, high specific capacity upon charge ordischarge, high coulombic efficiency, excellent retention of specificcapacity and energy density over several cycles of charging anddischarging, high rate capability, reduced electrolyte decomposition,reduced resistance and its build-up during cycling, and improvedcalendar life. The electrolyte solutions provide these performancecharacteristics over a wide range of operational temperatures,encompassing about −40° C. or less and up to about 60° C., up to about80° C., or more. In some embodiments, these performance characteristicscan at least partially derive from the presence of a set of additives orcompounds, which can impart high voltage and high temperature stabilityto an electrolyte while retaining or improving battery performance.

For example, in terms of their stability, electrolytes that includecompounds according to some embodiments of the invention can undergolittle or no decomposition (beyond any initial decomposition related tofilm formation at battery electrodes or as part of initial cycling) whenbatteries incorporating the electrolytes are cycled at least up to aredox potential of a high voltage cathode material, such as at leastabout 4.2 V or about 4.5 V and up to about 4.95 V, up to about 5 V, upto about 5.5 V, up to about 6 V or more, as measured relative to alithium metal anode (Li/Li⁺ anode). These voltages may vary for othercounterelectrodes, but the improved performance is retained according tosome embodiments. Such reduction in electrolyte decomposition, in turn,yields one or more of the following benefits: (1) mitigation againstloss of electrolyte; (2) mitigation against the production ofundesirable by-products that can affect battery performance; (3)mitigation against the production of gaseous by-products that can affectbattery safety; and (4) reduced resistance and its build-up duringcycling.

Also, batteries incorporating the electrolyte solutions includingcompounds according to certain embodiments can exhibit high coulombicefficiency, as expressed in terms of a ratio of a specific capacity upondischarge to a specific capacity upon charge for a given cycle. Asmeasured upon cycling at a rate of 1 C (or another reference rate higheror lower than 1 C, such as 0.1 C, 0.05 C, 0.5 C, 5 C, or 10 C),batteries incorporating the improved electrolytes can have a coulombicefficiency at the 1^(st) cycle (or another initial cycle, such as the2^(nd) cycle, the 3^(rd) cycle, the 4^(th) cycle, the 5^(th) cycle, the6^(th) cycle, the 7^(th) cycle, the 8^(th) cycle, the 9^(th) cycle, orthe 10^(th) cycle) or an average coulombic efficiency over an initialset of cycles, such as cycles 1 through 3, cycles 1 through 5, cycles 3through 10, cycles 5 through 10, or cycles 5 through 15, that is atleast about 60%, such as at least about 70%, at least about 80%, atleast about 90%, or at least about 95%, and up to about 97%, up to about98%, up to about 99%, up to about 99.8%, up to about 99.9%, up to about99.99%, up to about 99.999%, or more. Stated in another way, and asmeasured upon cycling at a substantially constant current of 150 mA/g(or another reference current higher or lower than 150 mA/g, such as 15mA/g, 7.5 mA/g, 75 mA/g, 750 mA/g, or 1,500 mA/g), batteriesincorporating the electrolyte solutions including compounds of certainembodiments can have a coulombic efficiency at the 1^(st) cycle (oranother initial cycle, such as the 2^(nd) cycle, the 3^(rd) cycle, the4^(th) cycle, the 5^(th) cycle, the 6^(th) cycle, the 7^(th) cycle, the8^(th) cycle, the 9^(th) cycle, or the 10^(th) cycle) or an averagecoulombic efficiency over an initial set of cycles, such as cycles 1through 3, cycles 1 through 5, cycles 3 through 10, cycles 5 through 10,or cycles 5 through 15, that is at least about 60%, such as at leastabout 70%, at least about 80%, at least about 90%, or at least about95%, and up to about 97%, up to about 98%, up to about 99%, up to about99.8%, up to about 99.9%, up to about 99.99%, up to about 99.999%, ormore. The stated values for current can be per unit mass of a cathodeactive material, and can be expressed in units of mA/(g of the cathodeactive material).

In addition, batteries incorporating the electrolyte solutions includingcompounds of certain embodiments can exhibit excellent capacityretention defined in terms of a specific capacity (both upon charge andupon discharge) over several charging and discharging cycles, such that,after 100 cycles, after 200 cycles, after 300 cycles, after 400 cycles,after 500 cycles, after 600 cycles, after 1,000 cycles, or even after5,000 cycles from an initial cycle, at least about 50%, at least about60%, at least about 70%, at least about 75%, at least about 80%, or atleast about 85%, and up to about 90%, up to about 95%, up to about 98%,or more of an initial or maximum specific capacity at the 1^(st) cycle(or another initial cycle, such as the 2^(nd) cycle, the 3^(rd) cycle,the 4^(th) cycle, the 5^(th) cycle, the 6^(th) cycle, the 7^(th) cycle,the 8^(th) cycle, the 9^(th) cycle, or the 10^(th) cycle) is retained,as measured upon cycling at a rate of 1 C (or another reference ratehigher or lower than 1 C, such as 0.1 C, 0.05 C, 0.5 C, 5 C, or 10 C) orupon cycling at a substantially constant current of 150 mA/g (or anotherreference current higher or lower than 150 mA/g, such as 15 mA/g, 7.5mA/g, 75 mA/g, 750 mA/g, or 1,500 mA/g). The stated values for currentcan be per unit mass of a cathode active material, and can be expressedin units of mA/(g of the cathode active material).

In addition, batteries incorporating the electrolyte solutions includingcompounds of certain embodiments can exhibit excellent efficiencyretention defined in terms of a coulombic efficiency over severalcharging and discharging cycles, such that, after 100 cycles, after 200cycles, after 300 cycles, after 400 cycles, after 500 cycles, after 600cycles, after 1,000 cycles, or even after 5,000 cycles from an initialcycle, at least about 70%, at least about 80%, at least about 90%, or atleast about 95%, and up to about 97%, up to about 98%, up to about 99%,up to about 99.9%, or more of an initial or maximum coulombic efficiencyat the 1^(st) cycle (or another initial cycle, such as the 2^(nd) cycle,the 3^(rd) cycle, the 4^(th) cycle, the 5^(th) cycle, the 6^(th) cycle,the 7^(th) cycle, the 8^(th) cycle, the 9^(th) cycle, or the 10^(th)cycle) is retained, as measured upon cycling at a rate of 1 C (oranother reference rate higher or lower than 1 C, such as 0.1 C, 0.05 C,0.5 C, 5 C, or 10 C) or upon cycling at a substantially constant currentof 150 mA/g (or another reference current higher or lower than 150 mA/g,such as 15 mA/g, 7.5 mA/g, 75 mA/g, 750 mA/g, or 1,500 mA/g). The statedvalues for current can be per unit mass of a cathode active material,and can be expressed in units of mA/(g of the cathode active material).

In terms of rate capability or power performance, batteriesincorporating the electrolyte solutions including compounds of certainembodiments can exhibit excellent rate capability defined in terms ofretention of specific capacity (both upon charge and upon discharge)when charged, discharged, or cycled at higher rates, such that, asmeasured at a high rate of 1 C (or another high rate that is n times areference, low rate, with n>1 such as n=5, n=10, n=20, or n=100), atleast about 60%, at least about 70%, at least about 75%, at least about80%, at least about 85%, at least about 90%, or at least about 95%, andup to about 99%, up to about 99.5%, up to about 99.9%, or more of a lowrate or maximum specific capacity at a rate of 0.05 C (or anotherreference rate higher or lower than 0.05 C, such as 0.1 C) is retained.Stated in another way, batteries incorporating the electrolyte solutionsincluding compounds of certain embodiments can exhibit excellentretention of specific capacity (both upon charge and upon discharge)when charged, discharged, or cycled at higher currents, such that, asmeasured at a substantially constant current of 150 mA/g (or anothercurrent that is n times a reference current, with n>1 such as n=5, n=10,n=20, or n=100), at least about 60%, at least about 70%, at least about75%, at least about 80%, at least about 85%, at least about 90%, or atleast about 95%, and up to about 99%, up to about 99.5%, up to about99.9%, or more of a low rate or maximum specific capacity at asubstantially constant current of 7.5 mA/g (or another reference currenthigher or lower than 7.5 mA/g, such as 15 mA/g) is retained. The statedvalues for current can be per unit mass of a cathode active material,and can be expressed in units of mA/(g of the cathode active material).

Likewise, batteries incorporating the electrolyte solutions includingcompounds of certain embodiments can exhibit excellent rate capabilitydefined in terms of retention of energy density when cycled at higherrates, such that, as measured at a rate of 1 C (or another rate that isn times a reference rate, with n>1 such as n=5, n=10, n=20, or n=100),at least about 60%, at least about 70%, at least about 75%, at leastabout 80%, at least about 85%, at least about 90%, or at least about95%, and up to about 99%, up to about 99.5%, up to about 99.9%, or moreof a low rate or maximum coulombic efficiency at a rate of 0.05 C (oranother reference rate higher or lower than 0.05 C, such as 0.1 C) isretained. Stated in another way, batteries incorporating the electrolytesolutions including compounds of certain embodiments can exhibitexcellent retention of energy density when cycled at higher currents,such that, as measured at a substantially constant current of 150 mA/g(or another current that is n times a reference current, with n>1 suchas n=5, n=10, n=20, or n=100), at least about 60%, at least about 70%,at least about 75%, at least about 80%, at least about 85%, at leastabout 90%, or at least about 95%, and up to about 99%, up to about99.5%, up to about 99.9%, or more of a low rate or maximum coulombicefficiency at a substantially constant current of 7.5 mA/g (or anotherreference current higher or lower than 7.5 mA/g, such as 15 mA/g) isretained. The stated values for current can be per unit mass of acathode active material, and can be expressed in units of mA/(g of thecathode active material).

In addition, batteries incorporating the electrolyte solutions includingcompounds of certain embodiments can have a reduced resistance and areduced resistance build-up during cycling. Such reduced resistance, inturn, yields one or more of the following benefits: (1) efficientremoval of Li ions from electrodes; (2) higher specific capacity andhigher energy density; (3) reduced hysteresis in a voltage profilebetween charging and discharging; and (4) mitigation against temperatureincrease during cycling.

Advantageously, the electrolyte solutions including compounds of certainembodiments can provide these performance characteristics over a widerange of operational temperatures, such as when batteries incorporatingthe electrolyte solutions including compounds of certain embodiments arecharged, discharged, or cycled from about −40° C. to about 80° C., fromabout −40° C. to about 60° C., from about −40° C. to about 25° C., fromabout −40° C. to about 0° C., from about 0° C. to about 60° C., fromabout 0° C. to about 25° C., from about 25° C. to about 60° C., or otherranges encompassing temperatures greater than or below 25° C. Theimproved electrolytes also can provide these performance characteristicsover a wide range of operational voltages between a rated cut-offvoltage and a rated charge voltage, such as when the batteries arecharged, discharged, or cycled between voltage ranges encompassing about2 V to about 4.2 V, about 2 V to about 4.3 V, about 2 V to about 4.5 V,about 2 V to about 4.6 V, about 2 V to about 4.7 V, about 2 V to about4.95 V, about 3 V to about 4.2 V, about 3 V to about 4.3 V, about 3 V toabout 4.5 V, about 3 V to about 4.6 V, about 3 V to about 4.7 V, about 3V to about 4.9 V, about 2 V to about 6 V, about 3 V to about 6 V, about4.2 V to about 6 V, about 4.5 V to about 6 V, about 2 V to about 5.5 V,about 3 V to about 5.5 V, about 4.5 V to about 5.5 V, about 2 V to about5 V, about 3 V to about 5 V, about 4.5 V to about 5 V, or about 5 V toabout 6 V, as measured relative to a lithium metal anode (Li/Li⁺ anode).Stated in another way, the batteries incorporating the electrolytesolutions including compounds of certain embodiments have a rated chargevoltage of at least about 4.2 V, at least about 4.3 V, at least about4.5 V, at least about 4.6 V, at least about 4.7 V, or at least about 5V, and up to about 5.5 V, up to about 6 V or more, as measured relativeto anodes included within the batteries and upon charging at a rate of 1C (or another reference rate higher or lower than 1 C, such as 0.1 C,0.05 C, 0.5 C, 5 C, or 10 C) or upon charging at a substantiallyconstant current of 150 mA/g (or another reference current higher orlower than 150 mA/g, such as 15 mA/g, 7.5 mA/g, 75 mA/g, 750 mA/g, or1,500 mA/g). The batteries can be charged to the rated charge voltagewhile substantially retaining the performance characteristics specifiedabove, such as in terms of coulombic efficiency, retention of specificcapacity, retention of coulombic efficiency, and rate capability.

A high voltage electrolyte according to some embodiments of theinvention can be formed with reference to the formula:

base electrolyte+stabilizing compound(s)→high voltage electrolyte  (1)

A high temperature electrolyte according to some embodiments of theinvention can be formed with reference to the formula:

base electrolyte+stabilizing compound(s)→high temperatureelectrolyte  (2)

In formulas (1) and (2), the base electrolyte can include a set ofsolvents and a set of salts, such as a set of Li-containing salts in thecase of Li-ion batteries. Examples of suitable solvents includenonaqueous electrolyte solvents for use in Li-ion batteries, includingcarbonates, such as ethylene carbonate, dimethyl carbonate, ethyl methylcarbonate, propylene carbonate, methyl propyl carbonate, and diethylcarbonate; sulfones; silanes; nitriles; esters; ethers; and combinationsthereof. Additional examples of suitable solvents include thosediscussed in Xu et al., “Sulfone-based Electrolytes for Lithium-IonBatteries,” Journal of the Electrochemical Society, 149 (7) A920-A926(2002); and Nagahama et al., “High Voltage Performances of Li₂NiPO₄FCathode with Dinitrile-Based Electrolytes,” Journal of theElectrochemical Society, 157 (6) A748-A752 (2010); the disclosures ofwhich are incorporated herein by reference in their entirety. Examplesof suitable salts include Li-containing salts for use in Li-ionbatteries, such as lithium hexafluorophosphate (“LiPF₆”), lithiumperchlorate (“LiClO₄”), lithium tetrafluoroborate (“LiBF₄”), lithiumtrifluoromethane sulfonate (“LiCF₃SO₃”), lithium bis(trifluoromethanesulfonyl)imide (“LiN(CF₃SO₂)₂”), lithium bis(perfluoroethylsulfonyl)imide (“LiN(CF₃CF₂SO₂)₂”), lithium bis(oxalato)borate(“LiB(C₂O₄)₂”), lithium difluoro oxalato borate (“LiF₂BC₂O₄”), andcombinations thereof. Other suitable solvents and salts can be used toyield high voltage and high temperature electrolytes having lowelectronic conductivity, high Li ion solubility, low viscosity, highthermal stability, and other desirable characteristics.

In formulas (1) and (2), the stabilizing compound(s) is a set ofadditives that can correspond to a single additive, a pair of differentadditives, or a combination of three or more different additives.Examples of suitable stabilizing additives include silicon-containingcompounds, such as silanes, siloxanes, and other organosilicon compoundsincluding a SiX₄ moiety or a SiR₃ moiety. One or more of the stabilizingadditives described herein can be used in combination with one or moreconventional additives to impart improved performance characteristics.

Examples of suitable silicon-containing compounds include silanesrepresented with reference to the formula:

In formula (3), X₁, X₂, X₃, and X₄ can be the same or different, and, insome embodiments, at least one of X₁, X₂, X₃, and X₄ is an organic groupincluding from 1 to 20 carbon atoms. For other embodiments, at least oneof X₁, X₂, X₃, and X₄ is an organic group including more than 20 carbonatoms. X₁, X₂, X₃, and X₄ can be independently selected from, forexample, hydride group, halo groups, hydroxy group, thio group, alkylgroups, alkenyl groups, alkynyl groups, aryl groups, iminyl groups,alkoxy groups, alkenoxy groups, alkynoxy groups, aryloxy groups, carboxygroups, alkylcarbonyloxy groups, alkenylcarbonyloxy groups,alkynylcarbonyloxy groups, arylcarbonyloxy groups, alkylthio groups,alkenylthio groups, alkynylthio groups, arylthio groups, cyano groups,N-substituted amino groups, alkylcarbonylamino groups, N-substitutedalkylcarbonylamino groups, alkenylcarbonylamino groups, N-substitutedalkenyl carbonylamino groups, alkynylcarbonylamino groups, N-substitutedalkynylcarbonylamino groups, arylcarbonylamino groups, N-substitutedarylcarbonylamino groups, boron-containing groups, aluminum-containinggroups, silicon-containing groups (e.g., silyl groups and siloxygroups), phosphorus-containing groups, and sulfur-containing groups.

Examples of suitable silane compounds include, but are not limited to:1,2-Bis(chlorodimethylsilyl)ethane, Bis(trimethylsilylmethyl)sulfide,Tetrakis(trimethylsilyl)silane, Tetraethylsilane,4-(Trimethylsilyl)-3-butyn-2-one, Trivinylmethylsilane,Dimethyldichlorosilane, Hexamethyldisilane, Tris(trimethylsilyl)silane,Vinyl(trifluoromethyl)dimethylsilane, Tetravinylsilane,1,3-Bis[(trimethylsilyl)ethynyl]benzene,1,2-Bis(methyldifluorosilyl)ethane, 2,2-Bis-(trimethylsilyl)dithiane,Phenyltrimethoxysilane, Pentafluorophenyltriethoxysilane, andcombinations thereof.

According to certain embodiments, suitable silicon-containing compoundsaccording to formula (3) include compounds where at least one of X₁, X₂,X₃, and X₄ includes a nitrogen atom or group. X₁, X₂, X₃, and X₄ can bethe same or different, and, in some embodiments, at least one of X₁, X₂,X₃, and X₄ is an organic group including from 1 to 20 carbon atoms. Forother embodiments, at least one of X₁, X₂, X₃, and X₄ is an organicgroup including more than 20 carbon atoms. In some embodiments, at leastone of X₁, X₂, X₃, and X₄ includes an ether linkage, and, in otherembodiments, at least one of X₁, X₂, X₃, and X₄ includes a silicon atomor another heteroatom. X₁, X₂, X₃, and X₄ can be independently selectedfrom, for example, hydride group, hydroxy group, alkyl groups, alkenylgroups, alkynyl groups, aryl groups, iminyl groups, alkoxy groups,alkenoxy groups, alkynoxy groups, aryloxy groups, carboxy groups,alkylcarbonyloxy groups, alkenylcarbonyloxy groups, alkynylcarbonyloxygroups, arylcarbonyloxy groups, alkylthio groups, alkenylthio groups,alkynylthio groups, arylthio groups, cyano groups, N-substituted aminogroups, alkylcarbonylamino groups, N-substituted alkylcarbonylaminogroups, alkenylcarbonylamino groups, N-substituted alkenyl carbonylaminogroups, alkynylcarbonylamino groups, N-substituted alkynylcarbonylaminogroups, arylcarbonylamino groups, N-substituted arylcarbonylaminogroups, and heterocycle groups.

In certain preferred embodiments, X₁, X₂, and X₃ are alkyl groups, andin particular methyl groups. In certain preferred embodiments where eachof X₁, X₂, and X₃ are methyl groups, these silicon-containing compoundsare referred to as NTMS compounds after the silicon-nitrogen bond (“N”)and the trimethylsilyl (“TMS”) provided by each of X₁, X₂, and X₃ beingmethyl groups. As described in more detail below, NTMS compounds exhibitdesirable properties as additives according to certain embodiments ofthe invention.

Examples of suitable NTMS compounds include, but are not limited to:Bis(trimethylsilyl)carbodiimide, Trimethylsilylazide,Bis(trimethylsilyl)urea, N,O-Bis(trimethylsilyl)trifluoroacetamide,N,O-Bis(trimethylsilyl)acetamide, (N,N-Dimethylamino)triethylsilane,Methylsilatrane, Trimethylsilyl isocyanate, Tetraisocyanatosilane,1-Trimethylsilyl-1,2,4-triazole, 2-(Trimethylsilyl)thiazole,Heptamethyldisilazane, and combinations thereof.

According to certain embodiments, suitable silicon-containing compoundsaccording to formula (3) include compounds where at least one of X₁, X₂,X₃, and X₄ includes a carbon atom or group. X₁, X₂, X₃, and X₄ can bethe same or different, and, in some embodiments, at least one of X₁, X₂,X₃, and X₄ is an organic group including from 1 to 20 carbon atoms. Forother embodiments, at least one of X₁, X₂, X₃, and X₄ is an organicgroup including more than 20 carbon atoms. In some embodiments, at leastone of X₁, X₂, X₃, and X₄ includes an ether linkage, and, in otherembodiments, at least one of X₁, X₂, X₃, and X₄ includes a silicon atomor another heteroatom. X₁, X₂, X₃, and X₄ can be independently selectedfrom, for example, hydride group, hydroxy group, alkyl groups, alkenylgroups, alkynyl groups, aryl groups, iminyl groups, alkoxy groups,alkenoxy groups, alkynoxy groups, aryloxy groups, carboxy groups,alkylcarbonyloxy groups, alkenylcarbonyloxy groups, alkynylcarbonyloxygroups, arylcarbonyloxy groups, alkylthio groups, alkenylthio groups,alkynylthio groups, arylthio groups, cyano groups, N-substituted aminogroups, alkylcarbonylamino groups, N-substituted alkylcarbonylaminogroups, alkenylcarbonylamino groups, N-substituted alkenyl carbonylaminogroups, alkynylcarbonylamino groups, N-substituted alkynylcarbonylaminogroups, arylcarbonylamino groups, N-substituted arylcarbonylaminogroups, and heterocycle groups.

In certain preferred embodiments, X₁, X₂, and X₃ are alkyl groups, andin particular methyl groups. In certain preferred embodiments where eachof X₁, X₂, and X₃ are methyl groups, these silicon-containing compoundsare referred to as CTMS compounds after the silicon-carbon bond (“C”)and the trimethylsilyl (“TMS”) provided by each of X₁, X₂, and X₃ beingmethyl groups. As described in more detail below, CTMS compounds exhibitdesirable properties as additives according to certain embodiments ofthe invention.

Examples of suitable CTMS compounds include, but are not limited to:2-(Trimethylsilyl) thiazole, Bis(trimethylsilylmethyl)sulfide,1,3-Bis[(trimethylsilyl)ethynyl]benzene,4-(Trimethylsilyl)-3-butyn-2-one, 2,2-Bis-(trimethylsilyl)dithiane, andcombinations thereof.

According to certain embodiments, suitable silicon-containing compoundsaccording to formula (3) include compounds where at least one of X₁, X₂,X₃, and X, includes a fluorine atom or group. X₁, X₂, X₃, and X₄ can bethe same or different, and, in some embodiments, at least one of X₁, X₂,X₃, and X₄ is an organic group including from 1 to 20 carbon atoms. Forother embodiments, at least one of X₁, X₂, X₃, and X₄ is an organicgroup including more than 20 carbon atoms. In some embodiments, at leastone of X₁, X₂, X₃, and X₄ includes an ether linkage, and, in otherembodiments, at least one of X₁, X₂, X₃, and X, includes a silicon atomor another heteroatom. X₂, X₃, and X₄ can be independently selectedfrom, for example, hydride group, hydroxy group, alkyl groups, alkenylgroups, alkynyl groups, aryl groups, iminyl groups, alkoxy groups,alkenoxy groups, alkynoxy groups, aryloxy groups, carboxy groups,alkylcarbonyloxy groups, alkenylcarbonyloxy groups, alkynylcarbonyloxygroups, arylcarbonyloxy groups, alkylthio groups, alkenylthio groups,alkynylthio groups, arylthio groups, cyano groups, N-substituted aminogroups, alkylcarbonylamino groups, N-substituted alkylcarbonylaminogroups, alkenylcarbonylamino groups, N-substituted alkenyl carbonylaminogroups, alkynylcarbonylamino groups, N-substituted alkynylcarbonylaminogroups, arylcarbonylamino groups, N-substituted arylcarbonylaminogroups, and heterocycle groups.

Examples of compounds according to certain embodiments of the inventionin which X₄ includes a fluorine atom or group include, but are notlimited to: Tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane,1h,1h,2h,2h-Perfluorooctyltriethoxysilane,(Pentafluorophenyl)triethoxysilane,Bis(1h,1h,2h,2h-perfluoroooctyl)tetramethyldisiloxane,1,3-Bis(heptadecafluoro-1,1,2,2-tetrahydrodecyl)tetramethyldisiloxane,1,2-Bis(methyldifluorosilyl)ethane,1-3-Bis(trifluoropropyl)tetramethyldislioxane,Vinyl(trifluoromethyl)dimethylsilane, and combinations thereof.

In certain preferred embodiments, X₁, X₂, and X₃ are alkyl groups, andin particular methyl groups. In such preferred embodiments where each ofR₁, R₂, and R₃ are methyl groups, these silicon-containing compounds arereferred to as trimethylsilyl (“TMS”) compounds provided by each of X₁,X₂, and X₃ being methyl groups. TMS compounds that also contain afluorine atom or group can exhibit desirable properties as additivesaccording to certain embodiments of the invention.

Examples of suitable TMS compounds which also contain a fluorine atom orgroup include, but are not limited to: Trimethylsilyl trifluoroacetate,N,O-Bis(trimethylsilyl)trifluoroacetamide, and combinations thereof.

According to certain embodiments, suitable silicon-containing compoundsaccording to formula (3) include compounds where at least one of X₁, X₂,X₃, and X₄ includes an aromatic ring. X₁, X₂, X₃, and X, can be the sameor different, and, in some embodiments, at least one of X₁, X₂, X₃, andX₄ is an organic group including from 1 to 20 carbon atoms. For otherembodiments, at least one of X₁, X₂, X₃, and X₄ is an organic groupincluding more than 20 carbon atoms. In some embodiments, at least oneof X₁, X₂, X₃, and X₄ includes an ether linkage, and, in otherembodiments, at least one of X₁, X₂, X₃, and X₄ includes a silicon atomor another heteroatom. X₁, X₂, X₃, and X₄ can be independently selectedfrom, for example, hydride group, hydroxy group, alkyl groups, alkenylgroups, alkynyl groups, aryl groups, iminyl groups, alkoxy groups,alkenoxy groups, alkynoxy groups, aryloxy groups, carboxy groups,alkylcarbonyloxy groups, alkenylcarbonyloxy groups, alkynylcarbonyloxygroups, arylcarbonyloxy groups, alkylthio groups, alkenylthio groups,alkynylthio groups, arylthio groups, cyano groups, N-substituted aminogroups, alkylcarbonylamino groups, N-substituted alkylcarbonylaminogroups, alkenylcarbonylamino groups, N-substituted alkenyl carbonylaminogroups, alkynylcarbonylamino groups, N-substituted alkynylcarbonylaminogroups, arylcarbonylamino groups, N-substituted arylcarbonylaminogroups, and heterocycle groups.

Examples of compounds according to certain embodiments of the inventionin which X₄ includes an aromatic ring include, but are not limited to:1,3-Bis[(trimethylsilyl)ethynyl]benzene, Phenyltrimethoxysilane,Pentafluorophenyltriethoxysilane, and combinations thereof.

According to certain embodiments, suitable silicon-containing compoundsaccording to formula (3) include compounds where at least one of X₁, X₂,X₃, and X₄ includes one or more unsaturated bond. X₁, X₂, X₃, and X, canbe the same or different, and, in some embodiments, at least one of X₁,X₂, X₃, and X₄ is an organic group including from 1 to 20 carbon atoms.For other embodiments, at least one of X₁, X₂, X₃, and X₄ is an organicgroup including more than 20 carbon atoms. In some embodiments, at leastone of X₁, X₂, X₃, and X₄ includes an ether linkage, and, in otherembodiments, at least one of X₁, X₂, X₃, and X₄ includes a silicon atomor another heteroatom. X₂, X₃, and X₄ can be independently selectedfrom, for example, hydride group, hydroxy group, alkyl groups, alkenylgroups, alkynyl groups, aryl groups, iminyl groups, alkoxy groups,alkenoxy groups, alkynoxy groups, aryloxy groups, carboxy groups,alkylcarbonyloxy groups, alkenylcarbonyloxy groups, alkynylcarbonyloxygroups, arylcarbonyloxy groups, alkylthio groups, alkenylthio groups,alkynylthio groups, arylthio groups, cyano groups, N-substituted aminogroups, alkylcarbonylamino groups, N-substituted alkylcarbonylaminogroups, alkenylcarbonylamino groups, N-substituted alkenyl carbonylaminogroups, alkynylcarbonylamino groups, N-substituted alkynylcarbonylaminogroups, arylcarbonylamino groups, N-substituted arylcarbonylaminogroups, and heterocycle groups.

Examples of compounds according to certain embodiments of the inventionin which X₄ includes one or more unsaturated bond include, but are notlimited to: Bis(trimethylsilyl)carbodiimide,Tris(trimethylsilyloxy)ethylene, Isopropenoxytrimethylsilane,4-(Trimethylsilyl)-3-butyn-2-one, Trivinylmethylsilane,Trivinylmethoxysilane, Vinyl(trifluoromethyl)dimethylsilane,Bis(trimethylsilyl)itaconate, Hexavinyldisiloxane, Trivinylethoxysilane,Allyltris(trimethoxysilyloxy)silane,1,3-Bis[(trimethylsilyl)ethynyl]benzene, Phenyltrimethoxysilane,Pentafluorophenyltriethoxysilane, and combinations thereof.

According to certain embodiments, suitable silicon-containing compoundsaccording to formula (3) include compounds where at least one of X₁, X₂,X₃, and X₄ includes an oxygen atom or group. X₁, X₂, X₃, and X₄ can bethe same or different, and, in some embodiments, at least one of X₁, X₂,X₃, and X₄ is an organic group including from 1 to 20 carbon atoms. Forother embodiments, at least one of X₁, X₂, X₃, and X₄ is an organicgroup including more than 20 carbon atoms. In some embodiments, at leastone of X₁, X₂, X₃, and X₄ includes an ether linkage, and, in otherembodiments, at least one of X₁, X₂, X₃, and X₄ includes a silicon atomor another heteroatom. X₁, X₂, X₃, and X₄ can be independently selectedfrom, for example, hydride group, hydroxy group, alkyl groups, alkenylgroups, alkynyl groups, aryl groups, iminyl groups, alkoxy groups,alkenoxy groups, alkynoxy groups, aryloxy groups, carboxy groups,alkylcarbonyloxy groups, alkenylcarbonyloxy groups, alkynylcarbonyloxygroups, arylcarbonyloxy groups, alkylthio groups, alkenylthio groups,alkynylthio groups, arylthio groups, cyano groups, N-substituted aminogroups, alkylcarbonylamino groups, N-substituted alkylcarbonylaminogroups, alkenylcarbonylamino groups, N-substituted alkenyl carbonylaminogroups, alkynylcarbonylamino groups, N-substituted alkynylcarbonylaminogroups, arylcarbonylamino groups, N-substituted arylcarbonylaminogroups, and heterocycle groups.

Examples of compounds according to certain embodiments of the inventionin which X₄ includes an oxygen atom or group include, but are notlimited to: 1,3-Bis(trimethylsiloxy)-1,3-dimethyldisiloxane,Tris(trimethylsilyl)phosphate, Decamethyltetrasiloxane,(Tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane, Trimethylsilyltrifluoroacetate, Tris(trimethylsilyloxy)silane, Silicon tetraacetate,Tetramethyl orthosilicate, Decamethylcyclopentasiloxane,Tris(trimethylsilyloxy)ethylene, Ethoxytrimethylsilane,Octakis(dimethylsiloxy)-t8-silsesquioxane, Isopropenoxytrimethylsilane,Hexamethyldisiloxane, Phenyltrimethoxysilane,Pentafluorophenyltriethoxysilane, Hexamethylcyclotrisiloxane,Tris(trimethylsilyl)phosphite, N,O-Bis(trimethylsilyl)acetamide,Tris(trimethylsilyl) borate, Tetrakis(trimethylsilyloxy)silane,Tetrakis(dimethylsilyloxy)silane,Bis(tridecafluoro-1,1,2,2-tetrahydrooctyl)tetramethyldisiloxane,(Cyclohexenyloxy)trimethylsilane, Mono-(trimethylsilyl) phosphite,2-(3,4-Epoxycyclohexyl)ethyltrimethoxysilane, Trimethyl-n-propoxysilane,Methoxytrimethylsilane, Tetrakis(trimethylsiloxy)titanium,Bis(trimethoxysilylpropyl)urea,1,3-Bis(trifluoropropyl)tetramethyldisiloxane,Methacryloxypropylsilatrane, Triethoxysilylundecanal ethylene glycolacetal, Tris(trimethylsiloxy)antimony, Trivinylmethoxysilane,Tetradecamethylhexasiloxane, Methyltris(trimethylsiloxy)silane,Dodecamethylcyclohexasiloxane, Bis(trimethylsilyl)itaconate,Methylsilatrane, Hexavinyldisiloxane, 3-Ethylheptamethyltrisiloxane,1,3-Bis(heptadecafluoro-1,1,2,2-tetrahydrodecyl)tetramethyldisiloxane,Trivinylethoxysilane, 1,1,1,3,3-Pentamethyl-3-acetoxydisiloxane,Bis(trimethylsilyl)adipate, Allyltris(trimethoxysilyloxy)silane,Trimethylsilyl polyphosphate, Dodecamethylcyclohexasiloxane, andcombinations thereof.

In certain preferred embodiments, X₁, X₂, and X₃ are alkyl groups, andin particular methyl groups. In such preferred embodiments where each ofX₁, X₂, and X₃ are methyl groups, these silicon-containing compounds arereferred to as OTMS compounds after the silicon-oxygen bond (“O”) andthe trimethylsilyl (“TMS”) provided by each of X₁, X₂, and X₃ beingmethyl groups. As described in more detail below, OTMS compounds exhibitdesirable properties as additives according to certain embodiments ofthe invention.

Examples of suitable OTMS compounds include, but are not limited to:1,3-Bis(trimethylsiloxy)-1,3-dimethyldisiloxane,decamethyltetrasiloxane, Trimethylsilyl trifluoroacetate,Ethoxytrimethylsilane, Isopropenoxytrimethylsilane,Hexamethyldisiloxane, Tris(trimethylsilyl)phosphate,Tris(trimethylsilyl)phosphite, Tetrakis(trimethylsilyloxy)silane,Tetrakis(trimethylsilyloxy)silane, Tris(dimethylsilyloxy)ethylene,N,O-Bis(trimethylsilyl)acetamide, Tris(trimethylsilyl)borate,Bis(tridecafluoro-1,1,2,2-tetrahydrooctyl)tetramethyldisiloxaneTrimethyl-n-propoxysilane, (Cyclohexenyloxy)trimethylsilane,Mono-(trimethylsilyl)phosphite, Methoxytrimethylsilane,Tetrakis(trimethylsiloxy)titanium,1,3-Bis(trifluoropropyl)tetramethyldisiloxane,Tris(trimethylsiloxy)antimony, Trivinylmethoxysilane,Tetradecamethylhexasiloxane, Methyltris(trimethylsiloxy)silane,Dodecamethylcyclohexasiloxane, Bis(trimethylsilyl)itaconate,3-Ethylheptamethyltrisiloxane,1,3-Bis(heptadecafluoro-1,1,2,2-tetrahydrodecyl)tetramethyldisiloxane,1,1,1,3,3-Pentamethyl-3-acetoxydisiloxane, Bis(trimethylsilyl)adipate,Allyltris(trimethoxysilyloxy)silane, Trimethylsilyl polyphosphate, andcombinations thereof.

Desirable performance characteristics can be obtained by the inclusionof at least one A and at least one silicon-A bond in the silaneaccording to formula (3), where A is a carbon atom or a heteroatom, suchas one selected from boron, aluminum, silicon, phosphorus, sulfur,fluorine, chlorine, bromine, and iodine atoms. For example, at least oneof X₁, X₂, X₃, and X₄ can include A that is bonded to the silicon offormula (3), and remaining ones of X₁, X₂, X₃, and X₄ can beindependently selected from, for example, hydride group, hydroxy group,alkyl groups, alkenyl groups, alkynyl groups, aryl groups, iminylgroups, alkoxy groups, alkenoxy groups, alkynoxy groups, aryloxy groups,carboxy groups, alkylcarbonyloxy groups, alkenylcarbonyloxy groups,alkynylcarbonyloxy groups, arylcarbonyloxy groups, alkylthio groups,alkenylthio groups, alkynylthio groups, arylthio groups, cyano groups,N-substituted amino groups, alkylcarbonylamino groups, N-substitutedalkylcarbonylamino groups, alkenylcarbonylamino groups, N-substitutedalkenyl carbonylamino groups, alkynylcarbonylamino groups, N-substitutedalkynylcarbonylamino groups, arylcarbonylamino groups, and N-substitutedarylcarbonylamino groups. It is contemplated that multiple ones of X₁,X₂, X₃, and X₄ can each include A that is bonded to the silicon offormula (3), such that the silane according to formula (3) can includemultiple silicon-A bonds, such as in the range of 2 to 4 or 3 to 4. Itis also contemplated that multiple ones of X₁, X₂, X₃, and X₄ caninclude different and respective A's that are bonded to the silicon offormula (3), such that the silane according to formula (3) can includemultiple silicon-A bonds (with respect to the different A's), such as inthe range of 2 to 4 or 3 to 4. The number of silicon-A bonds can beincreased beyond 4, for example, by the inclusion of silicon andsilicon-A bonds within one or more of X₁, X₂, X₃, and X₄.

Desirable performance characteristics also can be obtained by theinclusion of at least one A and at least one silicon-O-A bond in thesilane according to formula (3), where O is oxygen, and A is a carbonatom or a heteroatom, such as one selected from boron, aluminum,silicon, phosphorus, and sulfur atoms. For example, at least one of X₁,X₂, X₃, and X₄ can include O-A that is bonded to the silicon of formula(3) via a silicon-O-A bond, and remaining ones of X₁, X₂, X₃, and X₄ canbe independently selected from, for example, hydride group, hydroxygroup, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, iminylgroups, alkoxy groups, alkenoxy groups, alkynoxy groups, aryloxy groups,carboxy groups, alkylcarbonyloxy groups, alkenylcarbonyloxy groups,alkynylcarbonyloxy groups, arylcarbonyloxy groups, alkylthio groups,alkenylthio groups, alkynylthio groups, arylthio groups, cyano groups,N-substituted amino groups, alkylcarbonylamino groups, N-substitutedalkylcarbonylamino groups, alkenylcarbonylamino groups, N-substitutedalkenyl carbonylamino groups, alkynylcarbonylamino groups, N-substitutedalkynylcarbonylamino groups, arylcarbonylamino groups, and N-substitutedarylcarbonylamino groups. It is contemplated that multiple ones of X₁,X₂, X₃, and X₄ can each include O-A that is bonded to the silicon offormula (3) via a silicon-O-A bond, such that the silane according toformula (3) can include multiple silicon-O-A bonds, such as in the rangeof 2 to 4 or 3 to 4. It is also contemplated that multiple ones of X₁,X₂, X₃, and X₄ can include different and respective A's that are bondedto the silicon of formula (3) via oxygen atoms, such that the silaneaccording to formula (3) can include multiple silicon-O-A bonds (withrespect to the different A's), such as in the range of 2 to 4 or 3 to 4.The number of silicon-O-A bonds can be increased beyond 4, for example,by the inclusion of silicon, oxygen, and silicon-O-A bonds within one ormore of X₁, X₂, X₃, and X₄.

In the case that A is boron, particular examples of silicon-containingcompounds according to formula (3) include silicon-containing boranesrepresented with reference to the formulas:

In formulas (4) through (7), R₁, R₂, and R₃ can correspond to X₁, X₂,and X₃ according to formula (3). R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉,R₁₀, and R₁₁ can be the same or different, and, in some embodiments, atleast one of R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, and R₁₁ is anorganic group including from 1 to 20 carbon atoms. For otherembodiments, at least one of R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀,and R₁₁ is an organic group including more than 20 carbon atoms. In someembodiments, at least one of R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀,and R₁₁ includes an ether linkage, and, in other embodiments, at leastone of R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, and R₁₁ includes asilicon atom or another heteroatom. R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉,R₁₀, and R₁₁ can be independently selected from, for example, hydridegroup, hydroxy group, alkyl groups, alkenyl groups, alkynyl groups, arylgroups, iminyl groups, alkoxy groups, alkenoxy groups, alkynoxy groups,aryloxy groups, carboxy groups, alkylcarbonyloxy groups,alkenylcarbonyloxy groups, alkynylcarbonyloxy groups, arylcarbonyloxygroups, alkylthio groups, alkenylthio groups, alkynylthio groups,arylthio groups, cyano groups, N-substituted amino groups,alkylcarbonylamino groups, N-substituted alkylcarbonylamino groups,alkenylcarbonylamino groups, N-substituted alkenyl carbonylamino groups,alkynylcarbonylamino groups, N-substituted alkynylcarbonylamino groups,arylcarbonylamino groups, and N-substituted arylcarbonylamino groups. Informula (7), R₁₂ is a bivalent, organic group including from 1 to 20carbon atoms in some embodiments, and, for other embodiments, R₁₂ is abivalent, organic group including more than 20 carbon atoms. R₁₂ can beselected from, for example, alkylene groups, alkenylene groups, andalkynylene groups.

In the case that A is aluminum, particular examples ofsilicon-containing compounds according to formula (3) include thoserepresented with reference to the formulas:

In formulas (8) through (11), R₁, R₂, and R₃ can correspond to X₁, X₂,and X₃ according to formula (3). R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉,R₁₀, and R₁₁ can be the same or different, and, in some embodiments, atleast one of R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, and R₁₁ is anorganic group including from 1 to 20 carbon atoms. For otherembodiments, at least one of R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀,and R₁₁ is an organic group including more than 20 carbon atoms. In someembodiments, at least one of R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀,and R₁₁ includes an ether linkage, and, in other embodiments, at leastone of R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, and R₁₁ includes asilicon atom or another heteroatom. R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉,R₁₀, and R₁₁ can be independently selected from, for example, hydridegroup, hydroxy group, alkyl groups, alkenyl groups, alkynyl groups, arylgroups, iminyl groups, alkoxy groups, alkenoxy groups, alkynoxy groups,aryloxy groups, carboxy groups, alkylcarbonyloxy groups,alkenylcarbonyloxy groups, alkynylcarbonyloxy groups, arylcarbonyloxygroups, alkylthio groups, alkenylthio groups, alkynylthio groups,arylthio groups, cyano groups, N-substituted amino groups,alkylcarbonylamino groups, N-substituted alkylcarbonylamino groups,alkenylcarbonylamino groups, N-substituted alkenyl carbonylamino groups,alkynylcarbonylamino groups, N-substituted alkynylcarbonylamino groups,arylcarbonylamino groups, and N-substituted arylcarbonylamino groups. Informula (II), R₁₂ is a bivalent, organic group including from 1 to 20carbon atoms in some embodiments, and, for other embodiments, R₁₂ is abivalent, organic group including more than 20 carbon atoms. R₁₂ can beselected from, for example, alkylene groups, alkenylene groups, andalkynylene groups.

In the case that A is carbon, particular examples of silicon-containingcompounds according to formula (3) include those represented withreference to the formulas:

In formulas (12) through (17), R₁, R₂, and R₃ can correspond to X₁, X₂,and X₃ according to formula (3). R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉,R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, and R₁₅ can be the same or different, and, insome embodiments, at least one of R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉,R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, and R₁₅ is an organic group including from 1 to20 carbon atoms. For other embodiments, at least one of R₁, R₂, R₃, R₄,R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, and R₁₅ is an organic groupincluding more than 20 carbon atoms. In some embodiments, at least oneof R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, and R₁₅includes an ether linkage, and, in other embodiments, at least one ofR₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, and R₁₅includes a silicon atom or another heteroatom. R₁, R₂, R₃, R₄, R₅, R₆,R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, and R₁₅ can be independentlyselected from, for example, hydride group, hydroxy group, alkyl groups,alkenyl groups, alkynyl groups, aryl groups, iminyl groups, alkoxygroups, alkenoxy groups, alkynoxy groups, aryloxy groups, carboxygroups, alkylcarbonyloxy groups, alkenylcarbonyloxy groups,alkynylcarbonyloxy groups, arylcarbonyloxy groups, alkylthio groups,alkenylthio groups, alkynylthio groups, arylthio groups, cyano groups,N-substituted amino groups, alkylcarbonylamino groups, N-substitutedalkylcarbonylamino groups, alkenylcarbonylamino groups, N-substitutedalkenyl carbonylamino groups, alkynylcarbonylamino groups, N-substitutedalkynylcarbonylamino groups, arylcarbonylamino groups, and N-substitutedarylcarbonylamino groups. In formulas (16) and (17), R₁₆ is a bivalent,organic group including from 1 to 20 carbon atoms in some embodiments,and, for other embodiments, R₁₆ is a bivalent, organic group includingmore than 20 carbon atoms. R₁₆ can be selected from, for example,alkylene groups, alkenylene groups, and alkynylene groups.

In the case that A is carbon, additional examples of silicon-containingcompounds according to formula (3) include those represented withreference to the

In formulas (18) and (19), R₁, R₂, and R₃ can correspond to X₁, X₂, andX₃ according to formula (3). R₁, R₂, R₃, R₄, R₅, R₆, and R₇ can be thesame or different, and, in some embodiments, at least one of R₁, R₂, R₃,R₄, R₅, R₆, and R₇ is an organic group including from 1 to 20 carbonatoms. For other embodiments, at least one of R₁, R₂, R₃, R₄, R₅, R₆,and R₇ is an organic group including more than 20 carbon atoms. In someembodiments, at least one of R₁, R₂, R₃, R₄, R₅, R₆, and R₇ includes anether linkage, and, in other embodiments, at least one of R₁, R₂, R₃,R₄, R₅, R₆, and R₇ includes a silicon atom or another heteroatom. R₁,R₂, R₃, R₄, R₅, R₆, and R₇ can be independently selected from, forexample, hydride group, hydroxy group, alkyl groups, alkenyl groups,alkynyl groups, aryl groups, iminyl groups, alkoxy groups, alkenoxygroups, alkynoxy groups, aryloxy groups, carboxy groups,alkylcarbonyloxy groups, alkenylcarbonyloxy groups, alkynylcarbonyloxygroups, arylcarbonyloxy groups, alkylthio groups, alkenylthio groups,alkynylthio groups, arylthio groups, cyano groups, N-substituted aminogroups, alkylcarbonylamino groups, N-substituted alkylcarbonylaminogroups, alkenylcarbonylamino groups, N-substituted alkenyl carbonylaminogroups, alkynylcarbonylamino groups, N-substituted alkynylcarbonylaminogroups, arylcarbonylamino groups, and N-substituted arylcarbonylaminogroups. In some embodiments, R₇ does not include any carbonyl group ofthe form —CO—, and, in other embodiments, R₇ does not include anysulfonyl group of the form —SO₂—.

In certain preferred embodiments, compounds of formula (19) alkyl groupscomprise R₁, R₂, and R₃. In some embodiments, R₁, R₂, and R₃ are methylgroups. Examples of such trimethylsilyl compounds in which R₇ is chosensuch that the compound comprises an ester include, but are not limitedto: Silicon tetraacetate, Bis(trimethylsilyl)itaconate,Bis(trimethylsilyl)adipate, 1,1,1,3,3-Pentamethyl-3-acetoxydisiloxane,Trimethylsilyl trifluoroacetate, and combinations thereof.

In the case that A is silicon, particular examples of silicon-containingcompounds according to formula (3) include silanes represented withreference to the

In formulas (20) through (25), R₁, R₂, and R₃ can correspond to X₁, X₂,and X₃ according to formula (3). R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉,R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, and R₁₅ can be the same or different, and, insome embodiments, at least one of R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉,R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, and R₁₅ is an organic group including from 1 to20 carbon atoms. For other embodiments, at least one of R₁, R₂, R₃, R₄,R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, and R₁₅ is an organic groupincluding more than 20 carbon atoms. In some embodiments, at least oneof R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, and R₁₅includes an ether linkage, and, in other embodiments, at least one ofR₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, and R₁₅includes a silicon atom or another heteroatom. R₁, R₂, R₃, R₄, R₅, R₆,R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, and R₁₅ can be independentlyselected from, for example, hydride group, hydroxy group, alkyl groups,alkenyl groups, alkynyl groups, aryl groups, iminyl groups, alkoxygroups, alkenoxy groups, alkynoxy groups, aryloxy groups, carboxygroups, alkylcarbonyloxy groups, alkenylcarbonyloxy groups,alkynylcarbonyloxy groups, arylcarbonyloxy groups, alkylthio groups,alkenylthio groups, alkynylthio groups, arylthio groups, cyano groups,N-substituted amino groups, alkylcarbonylamino groups, N-substitutedalkylcarbonylamino groups, alkenylcarbonylamino groups, N-substitutedalkenyl carbonylamino groups, alkynylcarbonylamino groups, N-substitutedalkynylcarbonylamino groups, arylcarbonylamino groups, and N-substitutedarylcarbonylamino groups. In formulas (24) and (25), R₁₆ is a bivalent,organic group including from 1 to 20 carbon atoms in some embodiments,and, for other embodiments, R₁₆ is a bivalent, organic group includingmore than 20 carbon atoms. R₁₆ can be selected from, for example,alkylene groups, alkenylene groups, and alkynylene groups. In someembodiments, the silanes according to formulas (20) through (25) arenon-polymeric and have molecular weights no greater than about 10,000daltons, such as no greater than about 5,000 daltons, no greater thanabout 4,000 daltons, no greater than about 3,000 daltons, no greaterthan about 2,000 daltons, no greater than about 1,000 daltons, nogreater than about 900 daltons, no greater than about 800 daltons, nogreater than about 700 daltons, no greater than about 600 daltons, or nogreater than about 500 daltons.

Examples of compounds according to certain embodiments of the inventionin which A is silicon include, but are not limited to:Decamethylcyclopentasiloxane, Octakis(dimethylsiloxy)-t8-silsesquioxane,Hexamethylcyclotrisiloxane, Octaphenyl-t8-silsesquioxane,Dodecamethylcyclohexasiloxane, and combinations thereof.

In the case that A is phosphorus, particular examples ofsilicon-containing compounds according to formula (3) include phosphinesrepresented with reference to the formulas:

In formulas (26) through (29), R₁, R₂, and R₃ can correspond to X₁, X₂,and X₃ according to formula (3). R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉,R₁₀, and R₁₁ can be the same or different, and, in some embodiments, atleast one of R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, and R₁₁ is anorganic group including from 1 to 20 carbon atoms. For otherembodiments, at least one of R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀,and R₁₁ is an organic group including more than 20 carbon atoms. In someembodiments, at least one of R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀,and R₁₁ includes an ether linkage, and, in other embodiments, at leastone of R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, and R₁₁ includes asilicon atom or another heteroatom. R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉,R₁₀, and R₁₁ can be independently selected from, for example, hydridegroup, hydroxy group, alkyl groups, alkenyl groups, alkynyl groups, arylgroups, iminyl groups, alkoxy groups, alkenoxy groups, alkynoxy groups,aryloxy groups, carboxy groups, alkylcarbonyloxy groups,alkenylcarbonyloxy groups, alkynylcarbonyloxy groups, arylcarbonyloxygroups, alkylthio groups, alkenylthio groups, alkynylthio groups,arylthio groups, cyano groups, N-substituted amino groups,alkylcarbonylamino groups, N-substituted alkylcarbonylamino groups,alkenylcarbonylamino groups, N-substituted alkenyl carbonylamino groups,alkynylcarbonylamino groups, N-substituted alkynylcarbonylamino groups,arylcarbonylamino groups, and N-substituted arylcarbonylamino groups. Informula (29), R₁₂ is a bivalent, organic group including from 1 to 20carbon atoms in some embodiments, and, for other embodiments, R₁₂ is abivalent, organic group including more than 20 carbon atoms. R₁₂ can beselected from, for example, alkylene groups, alkenylene groups, andalkynylene groups.

In the case that A is phosphorus, additional examples ofsilicon-containing compounds according to formula (3) includephosphoranes represented with reference to the formulas:

In formulas (30) through (37), R₁, R₂, and R₃ can correspond to X₁, X₂,and X₃ according to formula (3). R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉,R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, and R₁₉ can be the same ordifferent, and, in some embodiments, at least one of R₁, R₂, R₃, R₄, R₅,R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, and R₁₉ isan organic group including from 1 to 20 carbon atoms. For otherembodiments, at least one of R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀,R₁₁, R₁₂, R₁₃, R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, and R₁₉ is an organic groupincluding more than 20 carbon atoms; In some embodiments, at least oneof R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, R₁₈,R₁₆, R₁₇, R₁₈, and R₁₉ includes an ether linkage, and, in otherembodiments, at least one of R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀,R₁₁, R₁₂, R₁₃, R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, and R₁₉ includes a silicon atomor another heteroatom. R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁,R₁₂, R₁₃, R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, and R₁₉ can be independently selectedfrom, for example, hydride group, hydroxy group, alkyl groups, alkenylgroups, alkynyl groups, aryl groups, iminyl groups, alkoxy groups,alkenoxy groups, alkynoxy groups, aryloxy groups, carboxy groups,alkylcarbonyloxy groups, alkenylcarbonyloxy groups, alkynylcarbonyloxygroups, arylcarbonyloxy groups, alkylthio groups, alkenylthio groups,alkynylthio groups, arylthio groups, cyano groups, N-substituted aminogroups, alkylcarbonylamino groups, N-substituted alkylcarbonylaminogroups, alkenylcarbonylamino groups, N-substituted alkenyl carbonylaminogroups, alkynylcarbonylamino groups, N-substituted alkynylcarbonylaminogroups, arylcarbonylamino groups, and N-substituted arylcarbonylaminogroups. In formulas (35) through (37), R₂₀ is a bivalent, organic groupincluding from 1 to 20 carbon atoms in some embodiments, and, for otherembodiments, R₂₀ is a bivalent, organic group including more than 20carbon atoms. R₂₀ can be selected from, for example, alkylene groups,alkenylene groups, and alkynylene groups.

In the case that A is phosphorus, additional examples ofsilicon-containing compounds according to formula (3) include phosphatesand phosphate derivatives represented with reference to the formulas:

In formulas (38) through (41), R₁, R₂, and R₃ can correspond to X₁, X₂,and X₃ according to formula (3). R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉,R₁₀, and R₁₁ can be the same or different, and, in some embodiments, atleast one of R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, and R₁₁ is anorganic group including from 1 to 20 carbon atoms. For otherembodiments, at least one of R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀,and R₁₁ is an organic group including more than 20 carbon atoms. In someembodiments, at least one of R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀,and R₁₁ includes an ether linkage, and, in other embodiments, at leastone of R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, and R₁₁ includes asilicon atom or another heteroatom. R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉,R₁₀, and R₁₁ can be independently selected from, for example, hydridegroup, hydroxy group, alkyl groups, alkenyl groups, alkynyl groups, arylgroups, iminyl groups, alkoxy groups, alkenoxy groups, alkynoxy groups,aryloxy groups, carboxy groups, alkylcarbonyloxy groups,alkenylcarbonyloxy groups, alkynylcarbonyloxy groups, arylcarbonyloxygroups, alkylthio groups, alkenylthio groups, alkynylthio groups,arylthio groups, cyano groups, N-substituted amino groups,alkylcarbonylamino groups, N-substituted alkylcarbonylamino groups,alkenylcarbonylamino groups, N-substituted alkenyl carbonylamino groups,alkynylcarbonylamino groups, N-substituted alkynylcarbonylamino groups,arylcarbonylamino groups, and N-substituted arylcarbonylamino groups. Informula (41), R₁₂ is a bivalent, organic group including from 1 to 20carbon atoms in some embodiments, and, for other embodiments, R₁₂ is abivalent, organic group including more than 20 carbon atoms. R₁₂ can beselected from, for example, alkylene groups, alkenylene groups, andalkynylene groups.

A particular example of a phosphate according to formula (38) isTris(trimethylsilyl)phosphate represented with reference to the formula:

In formula (42), it is contemplated that one or more of the methylgroups can be modified, such as by substituting a constituent hydrogenatom with another chemical element or functional group, or can bereplaced by another alkyl group, an alkenyl group, an alkynyl group, oran aryl group, either in a substituted or an unsubstituted form. Otherfunctionalizations or modifications of the phosphate set forth informula (42) are contemplated. Other examples of compounds according tocertain embodiments of the invention in which A is phosphorus include,but are not limited to: Tris(trimethylsilyl)phosphate,Tris(trimethylsilyl)phosphite, Trimethylsilyl polyphosphate, andcombinations thereof.

In the case that A is sulfur, particular examples of silicon-containingcompounds according to formula (3) include sulfides represented withreference to the formulas:

(R₁R₂R₃Si)O—S—O(SiR₄R₅R₆)  (43)

(R₁R₂R₃Si)O—S—R₇  (44)

In formulas (43) and (44), R₁, R₂, and R₃ can correspond to X₁, X₂, andX₃ according to formula (3). R₁, R₂, R₃, R₄, R₅, R₆, and R₇ can be thesame or different, and, in some embodiments, at least one of R₁, R₂, R₃,R₄, R₅, R₆, and R₇ is an organic group including from 1 to 20 carbonatoms. For other embodiments, at least one of R₁, R₂, R₃, R₄, R₅, R₆,and R₇ is an organic group including more than 20 carbon atoms. In someembodiments, at least one of R₁, R₂, R₃, R₄, R₅, R₆, and R₇ includes anether linkage, and, in other embodiments, at least one of R₁, R₂, R₃,R₄, R₅, R₆, and R₇ includes a silicon atom or another heteroatom. R₁,R₂, R₃, R₄, R₅, R₆, and R₇ can be independently selected from, forexample, hydride group, hydroxy group, alkyl groups, alkenyl groups,alkynyl groups, aryl groups, iminyl groups, alkoxy groups, alkenoxygroups, alkynoxy groups, aryloxy groups, carboxy groups,alkylcarbonyloxy groups, alkenylcarbonyloxy groups, alkynylcarbonyloxygroups, arylcarbonyloxy groups, alkylthio groups, alkenylthio groups,alkynylthio groups, arylthio groups, cyano groups, N-substituted aminogroups, alkylcarbonylamino groups, N-substituted alkylcarbonylaminogroups, alkenylcarbonylamino groups, N-substituted alkenyl carbonylaminogroups, alkynylcarbonylamino groups, N-substituted alkynylcarbonylaminogroups, arylcarbonylamino groups, and N-substituted arylcarbonylaminogroups.

In the case that A is sulfur, additional examples of silicon-containingcompounds according to formula (3) include those represented withreference to the formulas:

In formulas (45) through (50), R₁, R₂, and R₃ can correspond to X₁, X₂,and X₃ according to formula (3). R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉,R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, and R₁₅ can be the same or different, and, insome embodiments, at least one of R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉,R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, and R₁₅ is an organic group including from 1 to20 carbon atoms. For other embodiments, at least one of R₁, R₂, R₃, R₄,R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, and R₁₅ is an organic groupincluding more than 20 carbon atoms. In some embodiments, at least oneof R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, and R₁₅includes an ether linkage, and, in other embodiments, at least one ofR₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, and R₁₅includes a silicon atom or another heteroatom. R₁, R₂, R₃, R₄, R₅, R₆,R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, and R₁₅ can be independentlyselected from, for example, hydride group, hydroxy group, alkyl groups,alkenyl groups, alkynyl groups, aryl groups, iminyl groups, alkoxygroups, alkenoxy groups, alkynoxy groups, aryloxy groups, carboxygroups, alkylcarbonyloxy groups, alkenylcarbonyloxy groups,alkynylcarbonyloxy groups, arylcarbonyloxy groups, alkylthio groups,alkenylthio groups, alkynylthio groups, arylthio groups, cyano groups,N-substituted amino groups, alkylcarbonylamino groups, N-substitutedalkylcarbonylamino groups, alkenylcarbonylamino groups, N-substitutedalkenyl carbonylamino groups, alkynylcarbonylamino groups, N-substitutedalkynylcarbonylamino groups, arylcarbonylamino groups, and N-substitutedarylcarbonylamino groups. In formulas (49) and (50), R₁₆ is a bivalent,organic group including from 1 to 20 carbon atoms in some embodiments,and, for other embodiments, R₁₆ is a bivalent, organic group includingmore than 20 carbon atoms. R₁₆ can be selected from, for example,alkylene groups, alkenylene groups, and alkynylene groups.

In the case that A is sulfur, additional examples of silicon-containingcompounds according to formula (3) include sulfoxides represented withreference to the formulas:

In formulas (51) and (52), R₁, R₂, and R₃ can correspond to X₁, X₂, andX₃ according to formula (3). R₁, R₂, R₃, R₄, R₅, R₆, and R₇ can be thesame or different, and, in some embodiments, at least one of R₁, R₂, R₃,R₄, R₅, R₆, and R₇ is an organic group including from 1 to 20 carbonatoms. For other embodiments, at least one of R₁, R₂, R₃, R₄, R₅, R₆,and R₇ is an organic group including more than 20 carbon atoms. In someembodiments, at least one of R₁, R₂, R₃, R₄, R₅, R₆, and R₇ includes anether linkage, and, in other embodiments, at least one of R₁, R₂, R₃,R₄, R₅, R₆, and R₇ includes silicon or another heteroatom. R₁, R₂, R₃,R₄, R₅, R₆, and R₇ can be independently selected from, for example,hydride group, hydroxy group, alkyl groups, alkenyl groups, alkynylgroups, aryl groups, iminyl groups, alkoxy groups, alkenoxy groups,alkynoxy groups, aryloxy groups, carboxy groups, alkylcarbonyloxygroups, alkenylcarbonyloxy groups, alkynylcarbonyloxy groups,arylcarbonyloxy groups, alkylthio groups, alkenylthio groups,alkynylthio groups, arylthio groups, cyano groups, N-substituted aminogroups, alkylcarbonylamino groups, N-substituted alkylcarbonylaminogroups, alkenylcarbonylamino groups, N-substituted alkenyl carbonylaminogroups, alkynylcarbonylamino groups, N-substituted alkynylcarbonylaminogroups, arylcarbonylamino groups, and N-substituted arylcarbonylaminogroups.

In the case that A is sulfur, additional examples of silicon-containingcompounds according to formula (3) include sulfonates represented withreference to the formulas:

In formulas (53) and (54), R₁, R₂, and R₃ can correspond to X₁, X₂, andX₃ according to formula (3). R₁, R₂, R₃, R₄, R₅, R₆, and R₇ can be thesame or different, and, in some embodiments, at least one of R₁, R₂, R₃,R₄, R₅, R₆, and R₇ is an organic group including from 1 to 20 carbonatoms. For other embodiments, at least one of R₁, R₂, R₃, R₄, R₅, R₆,and R₇ is an organic group including more than 20 carbon atoms. In someembodiments, at least one of R₁, R₂, R₃, R₄, R₅, R₆, and R₇ includes anether linkage, and, in other embodiments, at least one of R₁, R₂, R₃,R₄, R₅, R₆, and R₇ includes a silicon atom or another heteroatom. R₁,R₂, R₃, R₄, R₅, R₆, and R₇ can be independently selected from, forexample, hydride group, hydroxy group, alkyl groups, alkenyl groups,alkynyl groups, aryl groups, iminyl groups, alkoxy groups, alkenoxygroups, alkynoxy groups, aryloxy groups, carboxy groups,alkylcarbonyloxy groups, alkenylcarbonyloxy groups, alkynylcarbonyloxygroups, arylcarbonyloxy groups, alkylthio groups, alkenylthio groups,alkynylthio groups, arylthio groups, cyano groups, N-substituted aminogroups, alkylcarbonylamino groups, N-substituted alkylcarbonylaminogroups, alkenylcarbonylamino groups, N-substituted alkenyl carbonylaminogroups, alkynylcarbonylamino groups, N-substituted alkynylcarbonylaminogroups, arylcarbonylamino groups, and N-substituted arylcarbonylaminogroups.

A particular example of a sulfonate according to formula (54) includesR₇ as a halo substituted alkyl group, namely t-Butyldimethylsilyltrifluoromethane sulfonate represented with reference to the formula:

In formula (55), it is contemplated that one or more of the alkyl groupsand the alkylfluoride group can be modified, such as by substituting aconstituent hydrogen or fluorine atom with another chemical element orfunctional group, or can be replaced by another alkyl group, an alkenylgroup, an alkynyl group, or an aryl group, either in a substituted or anunsubstituted form. Other functionalizations or modifications of thesulfonate set forth in formula (55) are contemplated.

Further examples of suitable silicon-containing compounds includesilicon-containing polymers, such as a polyphosphate withsilicon-containing side groups represented with reference to theformula:

In formula (56), n is a non-negative integer that is at least one orgreater than one and represents the number of repeat units included inthe polyphosphate. For certain embodiments, n is in the range of 1 to10, such as 2 to 10, and, in other embodiments, n is at least 10, suchas at least 20, at least 50, at least 100, at least 500, or at least1,000, and up to 5,000, up to 10,000, up to 50,000, up to 100,000 ormore. R₁, R₂, R₃, R₄, and R₅ can be the same or different, and, in someembodiments, at least one of R₁, R₂, R₃, R₄, and R₅ is an organic groupincluding from 1 to 20 carbon atoms. For other embodiments, at least oneof R₁, R₂, R₃, R₄, and R₅ is an organic group including more than 20carbon atoms. In some embodiments, at least one of R₁, R₂, R₃, R₄, andR₅ includes an ether linkage, and, in other embodiments, at least one ofR₁, R₂, R₃, R₄, and R₅ includes a silicon atom or another heteroatom.R₁, R₂, R₃, R₄, and R₅ can be independently selected from, for example,hydride group, hydroxy group, alkyl groups, alkenyl groups, alkynylgroups, aryl groups, iminyl groups, alkoxy groups, alkenoxy groups,alkynoxy groups, aryloxy groups, carboxy groups, alkylcarbonyloxygroups, alkenylcarbonyloxy groups, alkynylcarbonyloxy groups,arylcarbonyloxy groups, alkylthio groups, alkenylthio groups,alkynylthio groups, arylthio groups, cyano groups, N-substituted aminogroups, alkylcarbonylamino groups, N-substituted alkylcarbonylaminogroups, alkenylcarbonylamino groups, N-substituted alkenyl carbonylaminogroups, alkynylcarbonylamino groups, N-substituted alkynylcarbonylaminogroups, arylcarbonylamino groups, and N-substituted arylcarbonylaminogroups.

Further, compounds of the various formulas (3) through (56) may beformulated as salts along with suitable ions. Such compounds can containany of the many substitutions described in the formulas (3) through (56)in order to interact with a counter-ion. Examples of suitablesilicon-containing salts include, but are not limited to: Calciummetasilicate, Tris[N,N-bis(trimethylsilyl)amide]erbium(III), Sodiumhexafluorosilicate, and combinations thereof.

It is understood that certain compounds fall into more than one familyor group as described in formulas (3) through (56) and the associateddescription. Many compounds of embodiments of the invention preferablycontain one or more TMS structures. Such TMS structures can facilitatethe appropriate decomposition of additives to improve the performance ofconventional electrolytes. Without being bound by a particular theory ormode of action, the presence of silicon in additives can facilitate theformation of a silicon-containing film, layer, coating, or region on orwithin electrode materials. Such film formation is described in moredetail below.

Referring back to formulas (1) and (2), an amount of a particularcompound can be expressed in terms of a weight percent of the compoundrelative to a total weight of the electrolyte solution (or wt. %). Forexample, an amount of a compound can be in the range of about 0.01 wt. %to about 30 wt. %, such as from about 0.05 wt. % to about 30 wt. %, fromabout 0.01 wt. % to about 20 wt. %, from about 0.2 wt. % to about 15 wt.%, from about 0.2 wt. % to about 10 wt. %, from about 0.2 wt. % to about5 wt. %, or from about 5 wt. % to about 10 wt. %, and, in the case of acombination of multiple compounds, a total amount of the compounds canbe in the range of about 0.01 wt. % to about 30 wt. %, such as fromabout 0.05 wt. % to about 30 wt. %, from about 0.01 wt. % to about 20wt. %, from about 0.2 wt. % to about 15 wt. %, from about 0.2 wt. % toabout 10 wt. %, from about 0.2 wt. % to about 5 wt. %, or from about 5wt. % to about 10 wt. %. An amount of a compound also can be expressedin terms of a ratio of the number of moles of the compound per unitsurface area of either, or both, electrode materials. For example, anamount of a compound can be in the range of about 10⁻⁷ mol/m² to about10⁻² mol/m², such as from about 10⁻⁷ mol/m² to about 10⁻⁵ mol/m², fromabout 10⁻⁵ mol/m² to about 10⁻³ mol/m², from about 10⁻⁶ mol/m² to about10⁻⁴ mol/m², or from about 10⁴ mol/m² to about 10⁻² mol/m². As furtherdescribed below, a compound can be consumed or can react, decompose, orundergo other modifications during initial battery cycling. As such, anamount of a compound can refer to an initial amount of the compound usedduring the formation of the electrolyte solutions according to formulas(1) or (2), or can refer to an initial amount of the additive within theelectrolyte solution prior to battery cycling (or prior to anysignificant amount of battery cycling).

Resulting performance characteristics of a battery can depend upon theidentity of a particular compound used to form the high voltageelectrolyte according to formulas (1) or (2), an amount of the compoundused, and, in the case of a combination of multiple compounds, arelative amount of each compound within the combination. Accordingly,the resulting performance characteristics can be fine-tuned or optimizedby proper selection of the set of compounds and adjusting amounts of thecompounds in formulas (1) or (2). For example, in the case of certainphosphates when used as an additive compound, such astris(trimethylsilyl)phosphate, a desirable amount of the compound can bein the range of about 0.5 wt. % to about 3 wt. %, such as from about 1wt. % to about 2 wt. %. Fine-tuning of an amount of an additive compoundcan depend upon factors such as battery configuration andcharacteristics of a cathode material or anode material.

The formation according to formulas (1) or (2) can be carried out usinga variety of techniques, such as by mixing the base electrolyte and theset of additives, dispersing the set of additives within the baseelectrolyte, dissolving the set of additives within the baseelectrolyte, or otherwise placing these components in contact with oneanother. The set of additives can be provided in a liquid form, apowdered form (or another solid form), or a combination thereof. The setof additives can be incorporated in the electrolyte solutions offormulas (1) or (2) prior to, during, or subsequent to battery assembly.

The electrolyte solutions described herein can be used for a variety ofbatteries containing a high voltage cathode or a low voltage cathode,and in batteries operated at high temperatures. For example, theelectrolyte solutions can be substituted in place of, or used inconjunction with, conventional electrolytes for Li-ion batteries foroperations at or above 4.2 V.

FIG. 1 illustrates a Li-ion battery 100 implemented in accordance withan embodiment of the invention. The battery 100 includes an anode 102, acathode 106, and a separator 108 that is disposed between the anode 102and the cathode 106. In the illustrated embodiment, the battery 100 alsoincludes a high voltage electrolyte 104, which is disposed between theanode 102 and the cathode 106 and remains stable during high voltagebattery cycling.

The operation of the battery 100 is based upon reversible intercalationand de-intercalation of Li ions into and from host materials of theanode 102 and the cathode 106. Other implementations of the battery 100are contemplated, such as those based on conversion chemistry. Referringto FIG. 1, the voltage of the battery 100 is based on redox potentialsof the anode 102 and the cathode 106, where Li ions are accommodated orreleased at a lower potential in the former and a higher potential inthe latter. To allow both a higher energy density and a higher voltageplatform to deliver that energy, the cathode 106 includes an activecathode material for high voltage operations at or above 4.2 V. Suitablehigh voltage cathode materials include those having a specific capacityof at least about 10 mAh/g, at least about 20 mAh/g, at least about 30mAh/g, at least about 40 mAh/g, or at least about 50 mAh/g, as measuredupon discharge at a rate of 0.1 C (or another reference rate higher orlower than 0.1 C, such as 0.05 C, 0.5 C, or 1 C) from about 6 V to about4.5 V, from about 6 V to about 5 V, from about 5.5 V to about 4.5 V, orfrom about 5 V to about 4.5 V relative to a lithium metal anode (Li/Li⁺anode) or other counterelectrode. Suitable high voltage cathodematerials also include those having a specific capacity of at leastabout 10 mAh/g, at least about 20 mAh/g, at least about 30 mAh/g, atleast about 40 mAh/g, or at least about 50 mAh/g, as measured upondischarge at a substantially constant current of 15 mA/g (or anotherreference current higher or lower than 15 mA/g, such as 7.5 mA/g, 75mA/g, or 150 mA/g) from about 6 V to about 4.5 V, from about 6 V toabout 5 V, from about 5.5 V to about 4.5 V, or from about 5 V to about4.5 V relative to a lithium metal anode (Li/Li⁺ anode) or othercounterelectrode. The stated values for specific capacity and currentcan be per unit mass of a cathode active material, and can be expressedin units of mAh/(g of the cathode active material) and mA/(g of thecathode active material), respectively. Examples of suitable highvoltage cathode materials include phosphates, fluorophosphates,fluorosulphates, fluorosilicates, spinels, Li-rich layered oxides, andcomposite layered oxides. Further examples of suitable cathode materialsinclude: spinel structure lithium metal oxides, layered structurelithium metal oxides, lithium-rich layered structured lithium metaloxides, lithium metal silicates, lithium metal phosphates, metalfluorides, metal oxides, sulfur, and metal sulfides. Examples ofsuitable anode materials include conventional anode materials used inLi-ion batteries, such as lithium, graphite (“Li_(x)C₆”), and othercarbon, silicate, or oxide-based anode materials.

For example, a class of suitable high voltage phosphates can berepresented as: Li_(a)(M1_(b)M2_(c)M3_(d)M4_(e))_(f)PO₄, where M1, M2,M3, and M4 can be the same or different, M1 is Mn, Co, or Ni, M2 is atransition metal, such as Ti, V, Cr, Mn, Fe, Co, Ni, Zr, Nb, or Mo, M3is a transition metal or a main group element, optionally excludingelements of Group VIA and Group VIIA, M4 is a transition metal or a maingroup element, optionally excluding elements of Group VIA and GroupVIIA, 1.2≧a≧0.9 (or 1.2>a>0.9), 1≧b≧0.6 (or 1>b>0.6), 0.4≧c≧0 (or0.4>c>0), 0.2≧d≧0 (or 0.2>d>0), 0.2≧e≧0 (or 0.2>e>0), and 1.2≧f≧0.9 (or1.2>f>0.9). Additional details regarding this class of cathode materialscan be found in Goodenough et al., “Challenges for Rechargeable LiBatteries,” Chemistry of Materials 22, 587-603 (2010); Marom et al., “Areview of advanced and practical lithium battery materials,” J. Mater.Chem., 21, 9938 (2011); Zhi-Ping et al., “Li-Site and Metal-Site IonDoping in Phosphate-Olivine LiCoPO₄ by First-Principles Calculation,”Chin. Phys. Lett. 26 (3) 038202 (2009); and Fisher et al., “LithiumBattery Materials LiMPO₄ (M) Mn, Fe, Co, and Ni): Insights into DefectAssociation, Transport Mechanisms, and Doping Behavior,” Chem. Mater.2008, 20, 5907-5915; the disclosures of which are incorporated herein byreference in their entirety.

For example, another class of suitable high voltage phosphates cancomprise lithium (Li), cobalt (Co), a first transition metal (M1), asecond transition metal (M2) different from M1, and phosphate (PO₄),where M1 and M2 are each selected from iron (Fe), titanium (Ti),vanadium (V), niobium (Nb), zirconium (Zr), hafnium (Hf), molybdenum(Mo), tantalum (Ta), tungsten (W), manganese (Mn), copper (Cu), chromium(Cr), nickel (Ni), and zinc (Zn) (e.g., as dopants and/or oxidesthereof), and can have molar ratios of Li:Co:M1:M2:PO₄ defined by(1−x):(1−y−z):y:z:(1−a), respectively, optionally represented (as ashorthand notation) as:Li_((1-x):)Co_((1-y-z):)M1_(y):M2_(z):(PO₄)_((1-a)), where −0.3≦x≦0.3;0.01≦y≦0.5; 0.01≦z≦0.3; −0.5≦a≦0.5; and 0.2≦1−y−z≦0.98. Preferably, M1and M2 are each selected from iron (Fe), titanium (Ti), vanadium (V) andniobium (Nb) (e.g., as dopants and/or oxides thereof). Preferably, M1 isiron (Fe) (e.g., as a dopant and/or oxide thereof), M2 is selected fromtitanium (Ti), vanadium (V), and niobium (Nb) (e.g., as dopants and/oroxides thereof). Preferably, −0.3≦x<0, −0.2≦x<0, or −0.1≦x<0.Preferably, M2 is Ti, and 0.05≦z≦0.25 or 0.05≦z≦0.2. Preferably, M2 isV, and 0.03≦z≦0.25 or 0.05≦z≦0.2. Preferably, 0.3≦1−y−z≦0.98,0.5≦1−y−z≦0.98, or 0.7≦1−y−z≦0.98. Additional details regarding thisclass of olivine cathode materials can be found in co-pending andco-owned U.S. Provisional Application No. 61/426,733, entitled “LithiumIon Battery Materials with Improved Properties” and filed on Dec. 23,2010, the disclosure of which is incorporated herein by reference in itsentirety.

For example, a class of suitable high voltage fluorophosphates can berepresented as: Li_(a)(M1_(b)M2_(c)M3_(d)M4_(e))_(f)PO₄F_(g), where M1,M2, M3, and M4 can be the same or different, M1 is Mn, Co, or Ni, M2 isa transition metal, such as Ti, V, Cr, Mn, Fe, Co, Ni, Zr, Nb, or Mo, M3is a transition metal or a main group element, optionally excludingelements of Group VIA and Group VIIA, M4 is a transition metal or a maingroup element, optionally excluding elements of Group VIA and GroupVIIA, 1.2≧a≧0.9 (or 1.2>a>0.9), 1≧b≧0.6 (or 1>b>0.6), 0.4≧c≧0 (or0.4>c>0), 0.2≧d≧0 (or 0.2>d>0), 0.2≧e≧0 (or 0.2>e>0), 1.2>f>0.9 (or1.2>f>0.9), and 1.2≧g≧0 (or 1.2>g>0).

For example, a class of suitable high voltage fluorosilicates can berepresented as: Li_(a)(M1_(b)M2_(c)M3_(d)M4_(e))_(f)SiO₄F, where M1, M2,M3, and M4 can be the same or different, M1 is Mn, Co, or Ni, M2 is atransition metal, such as Ti, V, Cr, Mn, Fe, Co, Ni, Zr, Nb, or Mo, M3is a transition metal or a main group element, optionally excludingelements of Group VIA and Group VIIA, M4 is a transition metal or a maingroup element, optionally excluding elements of Group VIA and GroupVIIA, 1.2≧a≧0.9 (or 1.2>a>0.9), 1≧b≧0.6 (or 1>b>0.6), 0.4≧c≧0 (or0.4>c>0), 0.2>d>0 (or 0.2>d>0), 0.2≧e≧0 (or 0.2>e>0), and 1.2≧f≧0.9 (or1.2>f>0.9).

For example, another class of suitable high voltage fluorosilicates canbe represented as: Li_(a)(M1_(b)M2_(c)M3_(d)M4_(e))_(f),SiO₄F_(g), whereM1, M2, M3, and M4 can be the same or different, M1 is Mn, Co, or Ni, M2is a transition metal, such as Ti, V, Cr, Mn, Fe, Co, Ni, Zr, Nb, or Mo,M3 is a transition metal or a main group element, optionally excludingelements of Group VIA and Group VIIA, M4 is a transition metal or a maingroup element, optionally excluding elements of Group VIA and GroupVIIA, 1.2≧a≧0.9 (or 1.2>a>0.9), 1≧b≧0.6 (or 1>b>0.6), 0.4≧c≧0 (or0.4>c>0), 0.2≧d≧0 (or 0.2>d>0), 0.2≧e≧0 (or 0.2>e>0), 1.2≧f≧0.9 (or1.2>f>0.9), and 1.2≧g≧0 (or 1.2>g>0).

For example, a class of suitable high voltage spinels can be representedas: Li_(a)(M1_(b)M2_(c)M3_(d)M4_(c))_(f)O₄, where M1, M2, M3, and M4 canbe the same or different, M1 is Mn or Fe, M2 is Mn, Ni, Fe, Co, or Cu,M3 is a transition metal, such as Ti, V, Cr, Mn, Fe, Co, Ni, Zr, Nb, orMo, and M4 is a transition metal or a main group element, optionallyexcluding elements of Group VIA and Group VIIA, 1.2≧a≧0.9 (or1.2>a>0.9), 1.7≧b≧1.2 (or 1.7>b>1.2), 0.8≧c≧0.3 (or 0.8>c>0.3), 0.1≧d≧0(or 0.1>d>0), 0.1≧e≧0 (or 0.1>e>0), and 2.2≧f≧1.5 (or 2.2>f>1.5).LMNO-type cathode materials, such as Li_(1.05)Mn_(1.5)Ni_(0.5)O₄ andLMO-type materials, such as LiMn₂O₄ are included in this class.Additional details regarding this class of cathode materials can befound in Goodenough et al., “Challenges for Rechargeable Li Batteries,”Chemistry of Materials 22, 587-603 (2010); Marom et al., “A review ofadvanced and practical lithium battery materials,” J. Mater. Chem., 21,9938 (2011); and Yi et al., “Recent developments in the doping ofLiNi_(0.5)Mn_(1.5)O₄ cathode material for 5 V lithium-ion batteries,”Ionics (2011) 17:383-389; the disclosures of which are incorporatedherein by reference in their entirety.

For example, a class of suitable high voltage, Li-rich layered oxidescan be represented as: Li(Li_(a)M1_(b)M2_(c)M3_(d)M4_(c))_(f)O₂, whereM1, M2, M3, and M4 can be the same or different, M1 is a transitionmetal, such as Mn, Fe, V, Co, or Ni, M2 is a transition metal, such asMn, Fe, V, Co, or Ni, M3 is a transition metal, such as Mn, Fe, V, Co,or Ni, M4 is a transition metal or a main group element, optionallyexcluding elements of Group VIA and Group VIIA, 0.4≧a≧0.05 (or0.4>a>0.05), 0.7≧b≧0.1 (or 0.7>b>0.1), 0.7≧c≧0.1 (or 0.7>c>0.1),0.7≧d≧0.1 (or 0.7>d>0.1), 0.2>e>0 (or 0.2>e>0), and 1.2≧f≧0.9 (or1.2>f>0.9). OLO-type cathode materials are included in this class.Additional details regarding this class of cathode materials can befound in Goodenough et al., “Challenges for Rechargeable Li Batteries,”Chemistry of Materials 22, 587-603 (2010); Marom et al., “A review ofadvanced and practical lithium battery materials” J. Mater. Chem., 21,9938 (2011); Johnson et al., “Synthesis, Characterization andElectrochemistry of Lithium Battery Electrodes: xLi₂MnO₃(1−x)LiMn_(0.333)Ni_(0.333)Co_(0.333)O₂ (0<x<0.7),” Chem. Mater., 20,6095-6106 (2008); and Kang et al., “Interpreting the structural andelectrochemical complexity of 0.5Li₂MnO₃.0.5LiMO₂ electrodes for lithiumbatteries (M=Mn_(0.5-x)Ni_(0.5-x)Co_(2x), 0=x=0.5),” J. Mater. Chem.,17, 2069-2077 (2007); the disclosures of which are incorporated hereinby reference in their entirety.

For example, a class of suitable high voltage, composite layered oxidescan be represented as: (Li₂M1_(a)M2_(b)O₃)_(c)(LiM3_(d)M4_(e)M5_(f)O₂)_(g), where M1, M2, M3, M4, and M5 can be thesame or different, M1 is a transition metal, such as Mn, Fe, V, Co, orNi, M2 is a transition metal, such as Mn, Fe, V, Co, or Ni, M3 is atransition metal, such as Mn, Fe, V, Co, or Ni, M4 is a transitionmetal, such as Mn, Fe, V, Co, or Ni, M5 is a transition metal or a maingroup element, optionally excluding elements of Group VIA and GroupVIIA, 1.1≧a≧0 (or 1.1>a>0), 0.5>b>0 (or 0.5>b>0), 0.7>c>0 (or 0.7>c>0),1≧d≧0 (or 1>d>0), 1≧e≧0 (or 1>e>0), 1≧f≧0 (or 1>f>0), and 1≧g≧0.5 (or1>g>0.5). Additional details regarding this class of cathode materialscan be found in Goodenough et al., “Challenges for Rechargeable LiBatteries,” Chemistry of Materials 22, 587-603 (2010); Marom et al., “Areview of advanced and practical lithium battery materials,” J. Mater.Chem., 21, 9938 (2011); Johnson et al., “Synthesis, Characterization andElectrochemistry of Lithium Battery Electrodes: xLi₂MnO₃(1−x)LiMn_(0.333)Ni_(0.333)CO_(0.333)O₂ (0<x<0.7),” Chem. Mater., 20,6095-6106 (2008); and Kang et al., “Interpreting the structural andelectrochemical complexity of 0.5Li₂MnO₃.0.5LiM O₂ electrodes forlithium batteries (M=Mn_(0.5-x)Ni_(0.5-x)Co_(2x), 0=x=0.5),” J. Mater.Chem., 17, 2069-2077 (2007); the disclosures of which are incorporatedherein by reference in their entirety.

Attention next turns to FIG. 2, which illustrates operation of a Li-ionbattery and an illustrative, non-limiting mechanism of action of animproved electrolyte, according to an embodiment of the invention.Without being bound by a particular theory not recited in the claims,the inclusion of a set of one or more stabilizing additive compounds inan electrolyte solution can, upon operation of the battery (e.g., duringconditioning thereof) passivate a high voltage cathode material, therebyreducing or preventing reactions between bulk electrolyte components andthe cathode material that can degrade battery performance.

Referring to FIG. 2, an electrolyte 202 includes a base electrolyte,and, during initial battery cycling, components within the baseelectrolyte can assist in the in-situ formation of a protective film (inthe form of a solid electrolyte interface (“SEI”) 206) on or next to ananode 204. The anode SEI 206 can inhibit reductive decomposition of thehigh voltage electrolyte 202. Preferably, and without being bound bytheory not recited in the claims, for operation at voltages at or above4.2 V, the electrolyte 202 can also include a set of additives that canassist in the in-situ formation of a protective film (in the form of aSEI 208 or another derivative) on or next to a cathode 200. The cathodeSEI 208 can inhibit oxidative decomposition of the high voltageelectrolyte 202 that can otherwise occur during high voltage operations.As such, the cathode SEI 208 can inhibit oxidative reactions in acounterpart manner to the inhibition of reductive reactions by the anodeSEI 206. In the illustrated embodiment, the cathode SEI 208 can have athickness in the sub-micron range, and can include a set of one or morechemical elements corresponding to, or derived from, those present inthe set of one or more additives, such as silicon or other heteroatomincluded in the set of one or more additives. Advantageously, the set ofone or more additives can preferentially passivate the cathode 200 andcan selectively contribute towards film formation on the cathode 200,rather than the anode 204. Such preferential or selective film formationon the cathode 200 can impart stability against oxidative decomposition,with little or no additional film formation on the anode 204 (beyond theanode SEI 206) that can otherwise degrade battery performance throughresistive losses. More generally, the set of one or more additives candecompose below a redox potential of the cathode material and above aredox potential of SEI formation on the anode 204.

Without being bound by a particular theory not recited in the claims,the formation of the cathode SEI 208 can occur through one or more ofthe following mechanisms:

(1) The set of additive compounds can decompose to form the cathode SEI208, which inhibits further oxidative decomposition of electrolytecomponents.

(2) The set of additive compounds can form an intermediate product, suchas a complex with LiPF₆ or a cathode material, which intermediateproduct then decomposes to form the cathode SEI 208 that inhibitsfurther oxidative decomposition of electrolyte components.

(3) The set of additive compounds can form an intermediate product, suchas a complex with LiPF₆, which then decomposes during initial charging.The resulting decomposition product can then further decompose duringinitial charging to form the cathode SEI 208, which inhibits furtheroxidative decomposition of electrolyte components.

(4) The set of additive compounds can stabilize the cathode material bypreventing metal ion dissolution.

Other mechanisms of action of the electrolyte 202 are contemplated,according to an embodiment of the invention. For example, and in placeof, or in combination with, forming or improving the quality of thecathode SEI 208, the set of one or more additives or a derivativethereof (e.g., their decomposition product) can form or improve thequality of the anode SEI 206, such as to reduce the resistance for Liion diffusion through the anode SEI 206. As another example, the set ofone or more additives or a derivative thereof (e.g., their decompositionproduct) can improve the stability of the electrolyte 202 by chemicallyreacting or forming a complex with other electrolyte components. As afurther example, the set of one or more additives or a derivativethereof (e.g., their decomposition product) can scavenge decompositionproducts of other electrolyte components or dissolved electrodematerials in the electrolyte 202 by chemical reaction or complexformation. Any one or more of the cathode SEI 208, the anode SEI 206,and the other decomposition products or complexes can be viewed asderivatives, which can include a set of one or more chemical elementscorresponding to, or derived from, those present in the set of one ormore additives, such as silicon or other heteroatom included in the setof additives.

The electrolyte solutions described herein can be conditioned prior tosale or use in a commercial application. For example, batteriesincluding the electrolyte solutions can be conditioned by cycling priorto commercial sale or use in commerce. A method of conditioning abattery can, for example, include conditioning the battery forcommercial sale. Such method can include, for example, providing abattery, and cycling such battery through at least 1, at least 2, atleast 3, at least 4, or at least 5 cycles, each cycle including chargingthe battery and discharging the battery at a rate of 0.05 C (e.g., acurrent of 7.5 mA/g) between 4.95 V and 2.0 V (or another voltage range)versus a reference counterelectrode, such as a graphite anode. Chargingand discharging can be carried out at a higher or lower rate, such as ata rate of 0.1 C (e.g., a current of 15 mA/g), at a rate of 0.5 C (e.g.,a current of 75 mA/g), or at a rate of 1 C (e.g., a current of 150mA/g).

The electrochemical stability of the electrolyte in battery cells can beassessed by measuring the residual current, or the current that passesthrough the cell after the battery is fully charged or discharged.Residual current can be measured by fully charging the cell and thenapplying a voltage above the equilibrium potential. As the cell is fullycharged, the residual current reflects the extent of electrochemicaldecomposition of the materials in the cell. A low residual current ascompared to control demonstrates enhanced electrochemical stability.Without being bound to a particular theory or mode of action, above theequilibrium potential of the cell the electrochemical decomposition ofelectrolytes will allow current to flow in a battery cell due at leastin part to electron transfer from the negative electrode to theelectrolyte and from the electrolyte to the cathode. Additive compoundsaccording to embodiments of the invention improve the performance ofelectrolytes by any of the mechanisms proposed herein under conditionsthat may ordinarily cause electrolyte decomposition. Such improvementsin electrochemical stability help solve problems present in knownelectrolyte solutions.

As will be appreciated from the many examples that follow, additivecompounds of certain embodiments of the invention improve theperformance of conventional electrolytes in high voltage cells both atroom temperatures and at high temperatures. Further, compounds ofcertain embodiments of the invention improve the performance ofconventional electrolytes in low voltage cells at high temperatures.

Electrolytes containing certain OMTS additives have shown an improvementin residual current as compared to conventional electrolytes in standardCR2032 (Hohsen) coin cells. The cells were held at 4.5V, 4.9V and 5.1Vfor 10 hours at 50 degrees C. and the residual current was observed. Thelower residual current for the electrolytes containing certain OMTSadditives indicates reduction in electrolyte decomposition.

OTMS additives according to certain embodiments improve the coulombicefficiency over the control electrolyte in a high voltage cell. CertainOTMS additives have shown an improvement in coulombic efficiency of asmuch as about 6% as compared to the control electrolyte.

Certain OTMS additives have shown an improvement of as much as about 19%in room temperature cycle life of a high voltage spinel (LMNO-type)cathode material as compared to the control electrolyte.

NTMS additives according to certain embodiments improve the roomtemperature cycle life over the control electrolyte in a high voltagecell. Certain NTMS additives have shown an improvement of as much asabout 11% in room temperature cycle life of a high voltage spinel(LMNO-type) cathode material, as compared to the control electrolyte.

Certain TMS additives according to certain embodiments improve cyclelife and coulombic efficiency at higher additive concentrations thanthose used for certain OTMS and NTMS additives. Certain TMS additiveshave shown an improvement in coulombic efficiency of as much as about 3%as compared to the control electrolyte. Certain TMS additives have shownan improvement of as much as about 10% in room temperature cycle life ofa high voltage spinel (LMNO-type) cathode material as compared to thecontrol electrolyte.

Certain OTMS additives have shown an improvement of as much as about110% in high temperature cycle life of a high voltage spinel (LMNO-type)cathode material as compared to the control electrolyte. Certain OTMSadditives have shown an improvement of as much as about 200% in hightemperature cycle life of an LMO-type cathode material as compared tothe control electrolyte. Certain OTMS additives improve 1st cycleefficiency and cycle reversible capacity in a high voltage spinel(LMNO-type) cathode material as compared to the control electrolyte.

Certain OTMS additives have shown an improvement of as much as about 70%in high temperature cycle life of an NMC-type cathode material ascompared to the control electrolyte. OTMS additives according to certainembodiments improve the room temperature cycle life over the controlelectrolyte in a NMC-type cathode material.

Certain OTMS additives have shown an improvement of as much as about 70%in room temperature cycle life of lithiated layered oxide (OLO-type)cathode materials as compared to the control electrolyte. Certain OTMSadditives have shown an improvement of as much as about 130% in hightemperature cycle life of high voltage OLO-type cathode materials ascompared to the control electrolyte. Certain OTMS additives have shownan improvement of as much as about 2.5% in room temperature energyefficiency of high voltage OLO-type cathode materials as compared to thecontrol electrolyte.

Certain OTMS additives have shown an improvement of as much as about 18%in coulombic efficiency of a high voltage olivine cathode material(CM1-type) as compared to the control electrolyte. Certain OTMSadditives have shown an improvement of as much as about 400% in roomtemperature cycle life of a high voltage CM1-type cathode material ascompared to the control electrolyte.

NTMS additives according to certain embodiments improve the roomtemperature cycle life over the control electrolyte in a high voltagecell. Certain NTMS additives have shown an improvement of as much asabout 410% in room temperature cycle life of a high voltage CM1-typecathode material as compared to the control electrolyte.

EXAMPLES

The following examples describe specific aspects of some embodiments ofthe invention to illustrate and provide a description for those ofordinary skill in the art. The examples should not be construed aslimiting the invention, as the examples merely provide specificmethodology useful in understanding and practicing some embodiments ofthe invention.

Example 1 Methodology for Formation and Characterization of BatteryCells Including Stabilizing Additives

Battery cells were formed in a high purity argon filled glove box(M-Braun, O₂ and humidity content <0.1 ppm). Initially, poly(vinylidenefluoride) (Sigma Aldrich), carbon black (Super P Li, TIMCAL), and adoped LiCoPO₄ cathode material(Li_((1-x):)Co_((1-y-z):)Fe_(y):Ti_(z):(PO₄)_((1-a))) were mixed in1-methyl-2-pyrrolidinone (Sigma Aldrich), and the resulting slurry wasdeposited on an aluminum current collector and dried to form a compositecathode film. A lithium or graphite anode was used. In case of agraphite anode, a graphitic carbon (mesocarbon microbeads or MCMB) wasmixed with poly(vinylidene fluoride) (Sigma Aldrich), carbon black(Super P Li, TIMCAL), using 1-methyl-2-pyrrolidinone (Sigma Aldrich) asa solvent, and the resulting slurry was deposited on a copper currentcollector and dried to form a composite anode film. Each battery cellincluding the composite cathode film, a Millipore glass fiber or apolypropylene separator, and the lithium or graphite anode was assembledin a coin cell-type assembly (CR2025, Hohsen). A conventionalelectrolyte was mixed with a stabilizing additive compound and added tothe battery cell. The battery cell was sealed and cycled between aparticular voltage range (e.g., about 2 V to about 4.95 V) at aparticular temperature (e.g., room temperature or 25° C.).

Example 2 Characterization of Battery Cell Including StabilizingAdditive

Using the methodology of Example 1, performance characteristics weremeasured for a test battery cell including about 10 wt. % oftris(trimethylsilyl) phosphate as a stabilizing additive (labeled as“ttsp”) dispersed in a conventional electrolyte (ethylene carbonate,dimethyl carbonate, and 1M LiPF₆) and for a control battery cellincluding the conventional electrolyte but without the stabilizingadditive (labeled as “EC/DMC, 1M LiPF₆”). Each of the test battery celland the control battery cell included a doped LiCoPO₄ cathode material(Li_((1-x):)Co_((1-y-z):)Fe_(y):Ti_(z):(PO₄)_((1-a))). FIG. 3A (top)compares capacity retention with and without the stabilizing additiveover several cycles, expressed in terms of a percentage of an initialspecific capacity upon discharge retained at a particular cycle. As canbe appreciated, the inclusion of the stabilizing additive improved cyclelife, retaining about 78% of the initial discharge capacity after 26cycles (compared to below about 50% without the stabilizing additive).FIG. 3B (bottom) compares coulombic efficiency with and without thestabilizing additive over several cycles, with an inset providing amagnified view of measured values of coulombic efficiency with thestabilizing additive. As can be appreciated, the inclusion of thestabilizing additive improved coulombic efficiency, which increased froman initial value of about 95% and reached a plateau or steady-statevalue of about 97% (compared to values in the range of about 10% toabout 45% without the stabilizing additive).

Example 3 Characterization of Battery Cell Including StabilizingAdditive

Using the methodology of Example 1, performance characteristics weremeasured for a test battery cell including tris(trimethylsilyl)phosphateas a stabilizing additive (labeled as “ttsp”) dispersed in aconventional electrolyte (ethylene carbonate, ethyl methyl carbonate,and 1M LiPF₆) and for a control battery cell including the conventionalelectrolyte but without the stabilizing additive (labeled as “EC:EMC, 1MLiPF₆”). Each of the test battery cell and the control battery cellincluded a doped LiCoPO₄ cathode material(Li_((1-x):)Co_((1-y-z):)Fe_(y):Ti_(z):(PO₄)_((1-a))), and was cycledbetween about 2 V to about 4.95 V at a current of about 150 mA/g and atroom temperature (25° C.). FIG. 4 compares capacity retention with andwithout the stabilizing additive over several cycles, expressed in termsof a percentage of an initial specific capacity upon discharge retainedat a particular cycle. As can be appreciated, the inclusion of thestabilizing additive improved cycle life, retaining about 80% of theinitial discharge capacity after 100 cycles (compared to about 20%without the stabilizing additive) and about 68% of the initial dischargecapacity after 200 cycles (compared to under about 20% without thestabilizing additive). The inclusion of the stabilizing additive alsoimproved coulombic efficiency, retaining a value greater than about 98%after 100 cycles or more.

To assess stability at elevated temperatures, cycling was also carriedout at 50° C. FIG. 5 superimposes results of measurements of capacityretention at 50° C. onto FIG. 4. As can be appreciated, desirable cyclelife characteristics are retained at an elevated temperature of 50° C.

Example 4 Characterization of Battery Cell Including StabilizingAdditive

Using the methodology of Example 1, performance characteristics weremeasured for tris(trimethylsilyl)phosphate as a stabilizing additivedispersed in a conventional electrolyte (ethylene carbonate:ethyl methylcarbonate (1:2) and 1M LiPF₆). Each test battery cell included a dopedLiCoPO₄ cathode material(Li_((1-x):)Co_((1-y-z):)Fe_(y):Ti_(z):(PO₄)_((1-a))) and a graphiteanode. Measurements were carried out at different concentrations of thestabilizing additive, namely at about 0.25 wt. %, about 0.5 wt. %, about1 wt. %, about 2 wt. %, about 10 wt. %, and about 15 wt. %.

FIG. 6 is a plot of capacity retention (expressed in terms of apercentage of a specific capacity upon discharge at the 5^(th) cycleretained after 50 cycles) as a function of the concentration of thestabilizing additive. As can be appreciated, capacity retention variedwith the concentration of the stabilizing additive, ranging from about60% at a low concentration of the stabilizing additive to about 45% at ahigh concentration of the stabilizing additive and peaking at about 90%for an intermediate concentration of the stabilizing additive.

FIG. 7 is a plot of coulombic efficiency at the 50^(th) cycle as afunction of the concentration of the stabilizing additive. As can beappreciated, coulombic efficiency also varied with the concentration ofthe stabilizing additive, increasing from about 87% at a lowconcentration of the stabilizing additive to about 98% for anintermediate concentration of the stabilizing additive and exhibiting aslight decline for higher concentrations of the stabilizing additive.

Example 5 Characterization of Battery Cell Including StabilizingAdditive

Using the methodology of Example 1, cyclic voltammetry measurements werecarried out for 2 wt. % tris(trimethylsilyl)phosphate as a stabilizingadditive dispersed in a conventional electrolyte (ethylenecarbonate:ethyl methyl carbonate (1:2) and 1M LiPF₆). Measurements werecarried out for a battery cell including a LiMn₂O₄ cathode and a Lianode. FIG. 8 sets forth superimposed cyclic voltammograms for the1^(st) cycle through the 3^(rd) cycle, and FIG. 9 sets forthsuperimposed cyclic voltammograms for the 4^(th) cycle through the6^(th) cycle. As can be appreciated, a large resistance build-up isinitially observed during the charge phase of the 1^(st) cycle, and thisresistance decreases during subsequent cycles (as indicated by the arrowlabeled as “Resistance Decrease” in FIG. 8). Also, a peak at about 3.6 Vis initially observed during the discharge phase of the 1^(st) cycle,and this peak gradually disappears during subsequent cycles (asindicated by the dotted-line oval region labeled as “Peak Disappears” inFIG. 8). Without being bound by a particular theory not recited in theclaims, this transient behavior observed in the cyclic voltammograms canbe indicative of formation of intermediate products (e.g., derivativesof electrolyte additives) that may be involved (directly or indirectly)in the formation of a protective film (e.g., a cathode SEI) on acathode.

Example 6 Characterization of Battery Cell Including StabilizingAdditive

Performance characteristics were measured for a test battery cellincluding tris(trimethylsilyl)phosphate as a stabilizing additive(labeled as “ttsp”) dispersed in a conventional electrolyte (ethylenecarbonate, ethyl methyl carbonate, and 1M LiPF₆) and for a controlbattery cell including the conventional electrolyte but without thestabilizing additive (labeled as “EC:EMC(1:2), 1M LiPF₆”). Each of thetest battery cell and the control battery cell included a doped LiCoPO₄cathode material (Li_((1-x):)Co_((1-y-z)):Fe_(y):Ti_(z):(PO₄)_((1-a))),was kept in a fully charged state at about 50° C. for 8 days, and wascycled between about 2 V to about 4.95 V at a rate of about 1 C (150mA/g) and at room temperature (25° C.). FIG. 10 compares capacityretention with and without the stabilizing additive over several cycles,expressed in terms of a percentage of an initial specific capacity upondischarge retained at a particular cycle. As can be appreciated, theinclusion of the stabilizing additive improved cycle life subsequent toaging.

Example 7 Characterization of Battery Cells Including StabilizingAdditive

The effectiveness of tris(trimethylsilyl)phosphate as a stabilizingadditive was tested for other cathode materials. In one set of tests,performance characteristics were measured for a test battery cellincluding tris(trimethylsilyl)phosphate as a stabilizing additive(labeled as “ttsp”) dispersed in a conventional electrolyte (ethylenecarbonate, ethyl methyl carbonate, and 1M LiPF₆) and for a controlbattery cell including the conventional electrolyte but without thestabilizing additive (labeled as “EC:EMC(1:2), 1M LiPF₆”). Each of thetest battery cell and the control battery cell included aLiMn_(1.5)Ni_(0.5)O₄ cathode material, and was cycled between about 3 Vto about 4.9 V at a rate of about 1 C and about 50° C., after formationat room temperature. FIG. 11 compares capacity retention with andwithout the stabilizing additive over several cycles, expressed in termsof a percentage of an initial specific capacity upon discharge retainedat a particular cycle. As can be appreciated, the inclusion of thestabilizing additive improved cycle life for the LiMn_(1.5)Ni_(0.5)O₄cathode material.

In another set of tests, performance characteristics were measured for atest battery cell including tris(trimethylsilyl)phosphate as astabilizing additive (labeled as “ttsp”) dispersed in a conventionalelectrolyte (ethylene carbonate, ethyl methyl carbonate, and 1M LiPF₆)and for a control battery cell including the conventional electrolytebut without the stabilizing additive (labeled as “EC:EMC(1:2), 1MLiPF₆”). Each of the test battery cell and the control battery cellincluded a LiMn₂O₄ cathode material (about 4.2 V), and was cycledbetween about 3 V to about 4.5 V at a rate of about 1 C and about 50°C., after formation at room temperature. FIG. 12 compares capacityretention with and without the stabilizing additive over several cycles,expressed in terms of a percentage of an initial discharge capacityretained at a particular cycle. As can be appreciated, the inclusion ofthe stabilizing additive also improved cycle life for the LiMn₂O₄cathode material. The inclusion of the stabilizing additive also yieldedreduced self-discharge and a low residual current for the LiMn₂O₄cathode material, as can be appreciated with reference to FIG. 13 (whichsets forth open circuit voltage measurements at about 50° C., afterformation at room temperature) and FIG. 14 (which sets forth residualcurrent measurements at a constant voltage of about 5.1 V and at about50° C.).

Example 8 Characterization of Battery Cells Including StabilizingAdditives

Performance characteristics were measured for various stabilizingadditives dispersed in a conventional electrolyte (ethylene carbonate,dimethyl carbonate, and 1M LiPF₆). Each test battery cell and eachcontrol battery cell included a doped LiCoPO₄ cathode material(Li_((1-x):)Co_((1-y-z):)Fe_(y):Ti_(z):(PO₄)_((1-a))) and a lithiumanode.

FIG. 15 compares capacity retention with and withoutt-butyldimethylsilyl trifluoromethane sulfonate as a stabilizingadditive over several cycles, expressed in terms of a percentage of aninitial specific capacity upon discharge retained at a particular cycle.As can be appreciated, the inclusion of the stabilizing additivesimproved cycle life.

Example 9 Characterization of Battery Cells Including StabilizingAdditives

Using the methodology of Example 1, performance characteristics weremeasured for test battery cells including different stabilizingadditives dispersed in a conventional electrolyte (ethylene carbonate,ethyl methyl carbonate, and 1M LiPF₆) and for a control battery cellincluding the conventional electrolyte but without a stabilizingadditive. FIG. 16 compares capacity retention of the battery cells overseveral cycles, expressed in terms of a percentage of an initialspecific capacity upon discharge retained at a particular cycle. Twodifferent types of stabilizing additives were used. One type includedsilicon, and another type lacked silicon. A concentration of thestabilizing additives was about 2 wt. %. As can be appreciated, theinclusion of the silicon-containing stabilizing additives improved cyclelife, retaining more than about 80% of the initial discharge capacityafter 100 cycles compared to below about 65% without the stabilizingadditives. In this example, the non-silicon-containing stabilizingadditives deteriorated capacity retention to about 45% after 100 cycles.

Example 10 Characterization of Battery Cells Including StabilizingAdditives

Using the methodology of Example 1, performance characteristics weremeasured for silicon-containing stabilizing additives includingdifferent numbers of silicon-carbon bonds. FIG. 17 compares specificcapacity upon discharge at the 50^(th) cycle for battery cells includingthe stabilizing additives. As can be appreciated, the inclusion ofstabilizing additives including 3 or more silicon-carbon bonds yieldedhigher discharge capacities at the 50^(th) cycle compared to stabilizingadditives including less than 3 silicon-carbon bonds.

Example 11 Characterization of Battery Cells Including StabilizingAdditives

Using the methodology of Example 1, performance characteristics weremeasured for test battery cells including different silicon-containingstabilizing additives dispersed in a conventional electrolyte (ethylenecarbonate, ethyl methyl carbonate, and 1M LiPF₆) and for a controlbattery cell including the conventional electrolyte but without astabilizing additive. Each of the stabilizing additives tested includeda Si—O-A moiety, with A=P, B, or Si. FIG. 18 compares capacity retentionof the battery cells over several cycles, expressed in terms of apercentage of an initial specific capacity upon discharge retained at aparticular cycle. As can be appreciated, the inclusion of each of thestabilizing additives including the Si—O-A moiety improved cycle life.

Example 12 Characterization of Battery Cells Including StabilizingAdditives

Using the methodology of Example 1, performance characteristics weremeasured for test battery cells including different silicon-containingstabilizing additives dispersed in a conventional electrolyte (ethylenecarbonate, ethyl methyl carbonate, and 1M LiPF₆) and for a controlbattery cell including the conventional electrolyte but without astabilizing additive. FIG. 19 compares specific capacity upon dischargeat the 100^(th) cycle for the battery cells. A concentration of thestabilizing additives was about 2 wt. %. As can be appreciated, theinclusion of the silicon-containing stabilizing additives improveddischarge capacity.

Example 13 Characterization of Battery Cells Including StabilizingAdditives

Using the methodology of Example 1, performance characteristics weremeasured for battery cells including about 2 wt. %tris(trimethylsilyl)phosphate as a stabilizing additive (labeled as“TTSP”) dispersed in a conventional electrolyte (ethylene carbonate,ethyl methyl carbonate, and 1M LiPF₆) and including the conventionalelectrolyte but without the stabilizing additive (labeled as “EC:EMC(1:2), 1M LiPF₆”). To assess stability at reduced temperatures, cyclingwas carried out at about 10° C., about 0° C., and about −10° C., afterinitial cycling at room temperature (25° C.). FIG. 20 compares specificcapacity upon discharge of the battery cells over several cycles atdifferent temperatures. As can be appreciated, the inclusion of thestabilizing additive improved discharge capacity at temperatures belowroom temperature.

Example 14 Characterization of Battery Cells Including StabilizingAdditives

Using the methodology of Example 1, the effectiveness oftris(trimethylsilyl)phosphate as a stabilizing additive was tested forvarious cathode materials at an elevated temperature of about 50° C.FIG. 21 compares capacity retention at the 25^(th) cycle for batterycells including about 2 wt. % of the stabilizing additive (labeled as“TTSP”) dispersed in a conventional electrolyte (ethylene carbonate,ethyl methyl carbonate, and 1M LiPF₆) and including the conventionalelectrolyte but without the stabilizing additive (labeled as “EC:EMC(1:2 v), 1M LiPF₆”). As can be appreciated, the inclusion of thestabilizing additive improved capacity retention for each cathodematerial.

Example 15 Characterization of Battery Cells Including StabilizingAdditives

LiMn₂O₄ cathode films were assembled in half cells (including Li metalas an anode) in a coin cell-type assembly (CR2025, Hohsen). One cellincluded a conventional electrolyte (ethylene carbonate, ethyl methylcarbonate, and 1M LiPF₆) with tris(trimethylsilyl)phosphate (labeled as“TTSP”) as a stabilizing additive, and another cell included theconventional electrolyte without the stabilizing additive (labeled as“EC:EMC (1:2), 1M LiPF₆”). The cells were held at about 4.5V, about4.9V, and about 5.1V for about 10 hours at 50° C., and their residualcurrents were measured, with results illustrated in FIG. 22. As can beappreciated, the cells including tris(trimethylsilyl)phosphate had lowerresidual currents, which is indicative of a reduction in electrolytedecomposition.

Example 16 Characterization of Battery Cells Including StabilizingAdditives

Battery cells each including a LiMn_(0.5)Ni_(0.5)O₄ cathode material anda graphite anode (MCMB) were assembled using the methodology ofExample 1. One cell included a conventional electrolyte (ethylenecarbonate, ethyl methyl carbonate, and 1M LiPF₆) withtris(trimethylsilyl)phosphate (labeled as “TTSP”) as a stabilizingadditive, and another cell included the conventional electrolyte withoutthe stabilizing additive (labeled as “EC:EMC (1:2), 1M LiPF₆”). Thecells were cycled at a rate of about 0.1 C for several cycles, and theircolumbic efficiency was measured at every cycle, with resultsillustrated in FIG. 23. As can be appreciated, the inclusion oftris(trimethylsilyl)phosphate improved coulombic efficiency.

Example 17 Characterization of Battery Cells Including StabilizingAdditives

Battery cells each including a doped LiCoPO₄ cathode material and agraphite anode (MCMB) were assembled using the methodology of Example 1.One cell included a conventional electrolyte (ethylene carbonate, ethylmethyl carbonate, and 1M LiPF₆) with tris(trimethylsilyl)phosphate(labeled as “TTSP”) as a stabilizing additive, and another cell includedthe conventional electrolyte without the stabilizing additive (labeledas “EC:EMC (1:2), 1M LiPF₆”). The cells were initially cycled at roomtemperature (25° C.) and were then stored at about 50° C. for 8 days ina charged state. Subsequently, the cells were cooled to room temperatureand cycled again. FIG. 24 compares specific capacity upon discharge withand without the stabilizing additive over several cycles. As can beappreciated, the inclusion of tris(trimethylsilyl)phosphate improveddischarge capacity subsequent to storage at high temperatures, therebydemonstrating enhanced thermal stability of the electrolyte and/orbattery cells.

Example 18 Characterization of Battery Cells Including StabilizingAdditives

Battery cells each including a doped LiCoPO₄ cathode material(Li_((1-x):)Co_((1-y-z):)Fe_(y):Ti_(z):(PO₄)_((1-a))) and a graphiteanode (MCMB) were assembled using the methodology of Example 1. One cellincluded a conventional electrolyte (ethylene carbonate, ethyl methylcarbonate, and 1M LiPF₆) with tris(trimethylsilyl)phosphate (labeled as“TTSP”) as a stabilizing additive, and another cell included theconventional electrolyte without the stabilizing additive (labeled as“EC:EMC (1:2), 1M LiPF₆”). Signature rate test was carried out at the101^(st) cycle, and rate capability of the battery cells was measured.FIG. 25 compares capacity retention of the battery cells at differentcharging and discharging rates, expressed in terms of a percentage of alow rate (0.05 C) specific capacity retained at a particular rate. Ascan be appreciated, the inclusion of tris(trimethylsilyl)phosphateimproved rate capability both during charging and discharging.

Example 19 Characterization of Battery Cells Including StabilizingAdditives

Battery cells each including a LiMn_(1.5)Ni_(0.5)O₄ cathode material anda graphite anode (MCMB) were assembled using the methodology ofExample 1. One cell included a conventional electrolyte (ethylenecarbonate, ethyl methyl carbonate, and 1M LiPF₆) withtris(trimethylsilyl)phosphate as a stabilizing additive, and anothercell included the conventional electrolyte without the stabilizingadditive (labeled as “EC:EMC (1:2), 1M LiPF₆”). The cells were cycled ata rate of about 0.1 C for several cycles. FIG. 26 compares capacityretention with and without the stabilizing additive. As can beappreciated, the inclusion of tris(trimethylsilyl)phosphate improvedcapacity retention.

Example 20 Characterization of Battery Cells Including StabilizingAdditives

Battery cells each including a doped LiCoPO₄ cathode material(Li_((1-x):)Co_((1-y-z):)Fe_(y):Ti_(z):(PO₄)_((1-a))) and a graphiteanode (MCMB) were assembled using the methodology of Example 1. One cellincluded a conventional electrolyte (ethylene carbonate, ethyl methylcarbonate, and 1M LiPF₆) with about 2 wt. % oftris(trimethylsilyl)phosphate as a stabilizing additive, and anothercell included the conventional electrolyte without the stabilizingadditive (labeled as “EC:EMC (1:2), 1M LiPF₆”). The cells were cycled atroom temperature (25° C.), and their voltage profiles at the 1^(st) and100^(th) cycles during charging are set forth in FIG. 27. Higher voltageduring charging is indicative of a resistance build-up. As can beappreciated, the inclusion of tris(trimethylsilyl)phosphate yielded areduced cell resistance.

Example 21 Characterization of Battery Cells Including StabilizingAdditives

Half cells (including Li metal as an anode) were assembled using themethodology of Example 1. One cell included a conventional electrolyte(ethylene carbonate, ethyl methyl carbonate, and 1M LiPF₆) with about 2wt. % of tris(trimethylsilyl)phosphate (labeled as “TTSP”) as astabilizing additive, and another cell included the conventionalelectrolyte without the stabilizing additive (labeled as “EC:EMC (1:2),1M LiPF₆”). The cells were cycled at room temperature (25° C.), andtheir voltage profiles at the 3^(rd) cycle during discharging are setforth in FIG. 28. As can be appreciated, the inclusion oftris(trimethylsilyl)phosphate yielded a reduced cell resistance.

Example 22 Methodology for Formation and Characterization of BatteryCells Including Stabilizing Additives

Battery cells were formed in a high purity argon filled glove box(M-Braun, O₂ and humidity content <0.1 ppm). Initially, poly(vinylidenefluoride) (Sigma Aldrich), carbon black (Super P Li, TIMCAL), and acathode material were mixed in 1-methyl-2-pyrrolidinone (Sigma Aldrich),and the resulting slurry was deposited on an aluminum current collectorand dried to form a composite cathode film. A lithium or graphite anodewas used. In case of a graphite anode, a graphitic carbon was mixed withpoly(vinylidene fluoride) (Sigma Aldrich), carbon black (Super P Li,TIMCAL), using 1-methyl-2-pyrrolidinone (Sigma Aldrich) as a solvent,and the resulting slurry was deposited on a copper current collector anddried to form a composite anode film. Each battery cell including thecomposite cathode film, a Millipore glass fiber or a polypropyleneseparator, and the lithium or graphite anode was assembled in a coincell-type assembly (CR2025, Hohsen). Cells with Li anodes are tested inHohsen CR2032 cells. A conventional electrolyte was mixed with astabilizing additive and added to the battery cell. The battery cell wassealed and cycled between a particular voltage range for each cathode ata particular temperature (e.g., room temperature or 25° C.). Table 1shows cycling voltage range for each cathode in full cell. The uppercutoff voltage is 0.05V higher in a half cell than in a full cell.

TABLE 1 Cycling voltage range in full cell for different cathode CathodeCycling voltage, V LMNO-type 3-4.85 CM1-type 3-4.9  LMO-type 3-4.45NMC-type 3-4.1  NMC-type 3-4.45 OLO-type 2-4.6 

Example 23 Characterization of Battery Cells Including StabilizingAdditives

Using the methodology of Example 22, performance characteristics weremeasured for test battery cells including different silicon-containingstabilizing additives dispersed in a conventional electrolyte (ethylenecarbonate, ethyl methyl carbonate, and 1M LiPF₆) and for a controlbattery cell including the conventional electrolyte but without astabilizing additive. In this example, the cathode material wasLMNO-type. FIG. 29 compares coulombic efficiency of the battery cells atthe first cycle. It can be appreciated that several OTMS additivesperformed better than control.

Example 24 Characterization of Battery Cells Including StabilizingAdditives

Using the methodology of Example 22, performance characteristics weremeasured for test battery cells including different silicon-containingstabilizing additives dispersed in a conventional electrolyte (ethylenecarbonate, ethyl methyl carbonate, and 1M LiPF₆) and for a controlbattery cell including the conventional electrolyte but without astabilizing additive. In this example, the cathode material wasLMNO-type and the test was performed at room temperature. FIG. 30compares capacity retention of the battery cells over several cycles,expressed in terms of a percentage of an initial specific capacity upondischarge retained at a particular cycle. It can be appreciated thatseveral OTMS additives performed better than control.

Example 25 Characterization of Battery Cells Including StabilizingAdditives

Using the methodology of Example 22, performance characteristics weremeasured for test battery cells including different silicon-containingstabilizing additives dispersed in a conventional electrolyte (ethylenecarbonate, ethyl methyl carbonate, and 1M LiPF₆) and for a controlbattery cell including the conventional electrolyte but without astabilizing additive. In this example, the cathode material wasLMNO-type and the test was performed at room temperature. FIG. 31compares capacity retention of the battery cells over several cycles,expressed in terms of a percentage of an initial specific capacity upondischarge retained at a particular cycle. It can be appreciated thatseveral NTMS additives performed better than control.

Example 26 Characterization of Battery Cells Including StabilizingAdditives

Using the methodology of Example 22, performance characteristics weremeasured for test battery cells including different silicon-containingstabilizing additives dispersed in a conventional electrolyte (ethylenecarbonate, ethyl methyl carbonate, and 1M LiPF₆) and for a controlbattery cell including the conventional electrolyte but without astabilizing additive. In this example, the cathode material wasLMNO-type and the test was performed at room temperature. FIG. 32compares coulombic efficiency of the battery cells at the first cycle.It can be appreciated that several TMS additives performed better thancontrol.

Example 27 Characterization of Battery Cells Including StabilizingAdditives

Using the methodology of Example 22, performance characteristics weremeasured for test battery cells including different silicon-containingstabilizing additives dispersed in a conventional electrolyte (ethylenecarbonate, ethyl methyl carbonate, and 1M LiPF₆) and for a controlbattery cell including the conventional electrolyte but without astabilizing additive. In this example, the cathode material wasLMNO-type and the test was performed at room temperature. FIG. 33compares capacity retention of the battery cells over several cycles,expressed in terms of a percentage of an initial specific capacity upondischarge retained at a particular cycle. It can be appreciated thatseveral TMS additives performed better than control.

Example 28 Characterization of Battery Cells Including StabilizingAdditives

Using the methodology of Example 22, performance characteristics weremeasured for test battery cells including different silicon-containingstabilizing additives dispersed in a conventional electrolyte (ethylenecarbonate, ethyl methyl carbonate, and 1M LiPF₆) and for a controlbattery cell including the conventional electrolyte but without astabilizing additive. In this example, the cathode material wasCM1-type. FIG. 34 compares coulombic efficiency of the battery cells atthe first cycle. It can be appreciated that several OTMS additivesperformed better than control.

Example 29 Characterization of Battery Cells Including StabilizingAdditives

Using the methodology of Example 22, performance characteristics weremeasured for test battery cells including different silicon-containingstabilizing additives dispersed in a conventional electrolyte (ethylenecarbonate, ethyl methyl carbonate, and 1M LiPF₆) and for a controlbattery cell including the conventional electrolyte but without astabilizing additive. In this example, the cathode material wasCM1-type. FIG. 35 compares coulombic efficiency of the battery cells atthe first cycle. It can be appreciated that several OTMS additivesperformed better than control.

Example 30 Characterization of Battery Cells Including StabilizingAdditives

Using the methodology of Example 22, performance characteristics weremeasured for test battery cells including different silicon-containingstabilizing additives dispersed in a conventional electrolyte (ethylenecarbonate, ethyl methyl carbonate, and 1M LiPF₆) and for a controlbattery cell including the conventional electrolyte but without astabilizing additive. In this example, the cathode material was CM1-typethe test was performed at room temperature. FIG. 36 compares capacityretention of the battery cells over several cycles, expressed in termsof a percentage of an initial specific capacity upon discharge retainedat a particular cycle. It can be appreciated that several OTMS additivesperformed better than control.

Example 31 Characterization of Battery Cells Including StabilizingAdditives

Using the methodology of Example 22, performance characteristics weremeasured for test battery cells including different silicon-containingstabilizing additives dispersed in a conventional electrolyte (ethylenecarbonate, ethyl methyl carbonate, and 1M LiPF₆) and for a controlbattery cell including the conventional electrolyte but without astabilizing additive. In this example, the cathode material was CM1-typeand the test was performed at room temperature. FIG. 37 comparescapacity retention of the battery cells over several cycles, expressedin terms of a percentage of an initial specific capacity upon dischargeretained at a particular cycle. It can be appreciated that several OTMSadditives performed better than control.

Example 32 Characterization of Battery Cells Including StabilizingAdditives

Using the methodology of Example 22, performance characteristics weremeasured for test battery cells including different silicon-containingstabilizing additives dispersed in a conventional electrolyte (ethylenecarbonate, ethyl methyl carbonate, and 1M LiPF₆) and for a controlbattery cell including the conventional electrolyte but without astabilizing additive. In this example, the cathode material was CM1-typeand the test was performed at room temperature. FIG. 38 comparescapacity retention of the battery cells over several cycles, expressedin terms of a percentage of an initial specific capacity upon dischargeretained at a particular cycle. It can be appreciated that several NTMSadditives performed better than control.

Example 33 Characterization of Battery Cells Including StabilizingAdditives

Using the methodology of Example 22, performance characteristics weremeasured for test battery cells including different silicon-containingstabilizing additives dispersed in a conventional electrolyte (ethylenecarbonate, ethyl methyl carbonate, and 1M LiPF₆) and for a controlbattery cell including the conventional electrolyte but without astabilizing additive. In this example, the cathode material was NMC-typeand the test was performed at high temperature. FIG. 39 comparescapacity retention of the battery cells over several cycles, expressedin terms of a percentage of an initial specific capacity upon dischargeretained at a particular cycle. It can be appreciated that OTMSadditives performed better than control.

Example 34 Characterization of Battery Cells Including StabilizingAdditives

Using the methodology of Example 22, performance characteristics weremeasured for test battery cells including different silicon-containingstabilizing additives dispersed in a conventional electrolyte (ethylenecarbonate, ethyl methyl carbonate, and 1M LiPF₆) and for a controlbattery cell including the conventional electrolyte but without astabilizing additive. In this example, the cathode material was NMC-typeand the test was performed at high temperature. FIG. 40 comparescapacity retention of the battery cells over several cycles, expressedin terms of a percentage of an initial specific capacity upon dischargeretained at a particular cycle. It can be appreciated that OTMSadditives performed better than control.

Example 35 Characterization of Battery Cells Including StabilizingAdditives

Using the methodology of Example 22, performance characteristics weremeasured for test battery cells including different silicon-containingstabilizing additives dispersed in a conventional electrolyte (ethylenecarbonate, ethyl methyl carbonate, and 1M LiPF₆) and for a controlbattery cell including the conventional electrolyte but without astabilizing additive. In this example, the cathode material was OLO-typeand the test was performed at room temperature. FIG. 41 comparescapacity retention of the battery cells over several cycles, expressedin terms of a percentage of an initial specific capacity upon dischargeretained at a particular cycle. It can be appreciated that OTMSadditives performed better than control.

Example 36 Characterization of Battery Cells Including StabilizingAdditives

Using the methodology of Example 22, performance characteristics weremeasured for test battery cells including different silicon-containingstabilizing additives dispersed in a conventional electrolyte (ethylenecarbonate, ethyl methyl carbonate, and 1M LiPF₆) and for a controlbattery cell including the conventional electrolyte but without astabilizing additive. In this example, the cathode material was OLO-typeand the test was performed at high temperature. FIG. 42 comparescapacity retention of the battery cells over several cycles, expressedin terms of a percentage of an initial specific capacity upon dischargeretained at a particular cycle. It can be appreciated that OTMSadditives performed better than control.

Example 36 Characterization of Battery Cells Including StabilizingAdditives

Using the methodology of Example 22, performance characteristics weremeasured for test battery cells including different silicon-containingstabilizing additives dispersed in a conventional electrolyte (ethylenecarbonate, ethyl methyl carbonate, and 1M LiPF₆) and for a controlbattery cell including the conventional electrolyte but without astabilizing additive. In this example, the cathode material was OLO-typeand the test was performed at room temperature. FIG. 43 comparescapacity retention of the battery cells over several cycles, expressedin terms of a percentage of an initial specific capacity upon dischargeretained at a particular cycle. It can be appreciated that OTMSadditives performed better than control.

Example 37 Characterization of Battery Cells Including StabilizingAdditives

Using the methodology of Example 22, performance characteristics weremeasured for test battery cells including different silicon-containingstabilizing additives dispersed in a conventional electrolyte (ethylenecarbonate, ethyl methyl carbonate, and 1M LiPF₆) and for a controlbattery cell including the conventional electrolyte but without astabilizing additive. In this example, the cathode material was OLO-typeand the test was performed at room temperature. FIG. 44 compares energyefficiency of the battery cells over several cycles. It can beappreciated that OTMS additives performed better than control.

Example 38 Characterization of Battery Cells Including StabilizingAdditives

Using the methodology of Example 22, performance characteristics weremeasured for test battery cells including different silicon-containingstabilizing additives dispersed in a conventional electrolyte (ethylenecarbonate, ethyl methyl carbonate, and 1M LiPF₆) and for a controlbattery cell including the conventional electrolyte but without astabilizing additive. In this example, the cathode material wasLMNO-type and the test was performed at high temperature. FIG. 45compares capacity retention of the battery cells over several cycles,expressed in terms of a percentage of an initial specific capacity upondischarge retained at a particular cycle. It can be appreciated thatOTMS additives performed better than control.

Example 39 Characterization of Battery Cells Including StabilizingAdditives

Using the methodology of Example 22, performance characteristics weremeasured for test battery cells including different silicon-containingstabilizing additives dispersed in a conventional electrolyte (ethylenecarbonate, ethyl methyl carbonate, and 1M LiPF₆) and for a controlbattery cell including the conventional electrolyte but without astabilizing additive. In this example, the cathode material was LMO-typeand the test was performed at high temperature. FIG. 46 comparescapacity retention of the battery cells over several cycles, expressedin terms of a percentage of an initial specific capacity upon dischargeretained at a particular cycle. It can be appreciated that OTMSadditives performed better than control.

While the invention has been described with reference to the specificembodiments thereof, it should be understood by those skilled in the artthat various changes may be made and equivalents may be substitutedwithout departing from the true spirit and scope of the invention asdefined by the appended claims. In addition, many modifications may bemade to adapt a particular situation, material, composition of matter,method, or process to the objective, spirit and scope of the invention.All such modifications are intended to be within the scope of the claimsappended hereto. In particular, while the methods disclosed herein havebeen described with reference to particular operations performed in aparticular order, it will be understood that these operations may becombined, sub-divided, or re-ordered to form an equivalent methodwithout departing from the teachings of the invention. Accordingly,unless specifically indicated herein, the order and grouping of theoperations are not limitations of the invention.

1. A composition for use in an electrolyte solution, comprising: acompound represented by the formula (I):

wherein R₁, R₂, R₃, R₄, R₅, and R₆ are independently selected from thegroup consisting of substituted and unsubstituted C₁-C₂₀ alkyl groups,substituted and unsubstituted C₁-C₂₀ alkenyl groups, substituted andunsubstituted C₁-C₂₀ alkynyl groups, and substituted and unsubstitutedC₅-C₂₀ aryl groups; and X is selected from the group consisting ofcarbon, substituted and unsubstituted C₃-C₂₀ alkyl groups, substitutedand unsubstituted C₂-C₂₀ alkenyl groups, and substituted andunsubstituted C₄-C₂₀ alkynyl groups.
 2. The composition of claim 1wherein R₁, R₂, R₃, R₄, R₅, and R₆ are independently selected from thegroup consisting of substituted and unsubstituted C₁-C₂₀ alkyl groups.3. The composition of claim 1 wherein R₁, R₂, R₃, R₄, R₅, and R₆ areindependently selected from the group consisting of substituted andunsubstituted C₁-C₆ alkyl groups.
 4. The composition of claim 1 whereinR₁, R₂, R₃, R₄, R₅, and R₆ are independently selected from the groupconsisting of substituted and unsubstituted C₁ alkyl groups.
 5. Thecomposition of claim 1 wherein R₁, R₂, R₃, R₄, R₅, and R₆ are each C₁alkyl groups.
 6. The composition of claim 1 wherein X is selected fromthe group consisting of substituted and unsubstituted C₃-C₆ alkylgroups.
 7. The composition of claim 1 wherein X is selected from thegroup consisting of substituted and unsubstituted C₂-C₆ alkenyl groups.8. The composition of claim 1 wherein X is selected from the groupconsisting of substituted and unsubstituted C₄-C₁₂ alkynyl groups. 9.The composition of claim 1 wherein the compound is represented by theformula (II):


10. An electrolyte solution comprising: a salt; a solvent; and acompound represented by the formula (I):

wherein R₁, R₂, R₃, R₄, R₅, and R₆ are independently selected from thegroup consisting of substituted and unsubstituted C₁-C₂₀ alkyl groups,substituted and unsubstituted C₁-C₂₀ alkenyl groups, substituted andunsubstituted C₁-C₂₀ alkynyl groups, and substituted and unsubstitutedC₅-C₂₀ aryl groups; and X is selected from the group consisting ofcarbon, substituted and unsubstituted C₃-C₂₀ alkyl groups, substitutedand unsubstituted C₂-C₂₀ alkenyl groups, and substituted andunsubstituted C₄-C₂₀ alkynyl groups.
 11. The electrolyte solution ofclaim 10 wherein R₁, R₂, R₃, R₄, R₅, and R₆ are independently selectedfrom the group consisting of substituted and unsubstituted C₁-C₂₀ alkylgroups.
 12. The electrolyte solution of claim 10 wherein R₁, R₂, R₃, R₄,R₅, and R₆ are independently selected from the group consisting ofsubstituted and unsubstituted C₁-C₆ alkyl groups.
 13. The electrolytesolution of claim 10 wherein R₁, R₂, R₃, R₄, R₅, and R₆ areindependently selected from the group consisting of substituted andunsubstituted C₁ alkyl groups.
 14. The electrolyte solution of claim 10wherein R₁, R₂, R₃, R₄, R₅, and R₆ are each C₁ alkyl groups.
 15. Theelectrolyte solution of claim 10 wherein X is selected from the groupconsisting of substituted and unsubstituted C₃-C₆ alkyl groups.
 16. Theelectrolyte solution of claim 10 wherein X is selected from the groupconsisting of substituted and unsubstituted C₂-C₆ alkenyl groups. 17.The electrolyte solution of claim 10 wherein X is selected from thegroup consisting of substituted and unsubstituted C₄-C₁₂ alkynyl groups.18. The electrolyte solution of claim 10 wherein the compound isrepresented by the formula (II):


19. A method of making an electrolyte solution, comprising: providing anon-aqueous solvent; providing a lithium salt; and providing a compoundrepresented by the formula (I):

wherein R₁, R₂, R₃, R₄, R₅, and R₆ are independently selected from thegroup consisting of substituted and unsubstituted C₁-C₂₀ alkyl groups,substituted and unsubstituted C₁-C₂₀ alkenyl groups, substituted andunsubstituted C₁-C₂₀ alkynyl groups, and substituted and unsubstitutedC₅-C₂₀ aryl groups; and X is selected from the group consisting ofcarbon, substituted and unsubstituted C₃-C₂₀ alkyl groups, substitutedand unsubstituted C₂-C₂₀ alkenyl groups, and substituted andunsubstituted C₄-C₂₀ alkynyl groups; and combining the solvent, salt,and compound.
 20. The method of claim 19 wherein R₁, R₂, R₃, R₄, R₅, R₆and X are independently, selected from the group consisting ofsubstituted and unsubstituted C₁-C₆ alkyl groups.